CA3201921A1

CA3201921A1 - Treatment compositions with pro-fragrance silicone polymers that comprise heterocyclic moieties

Info

Publication number: CA3201921A1
Application number: CA3201921A
Authority: CA
Inventors: Sean Nicholas Natoli; Bernard William Kluesener; Rajan Keshav Panandiker; Gregory Scot Miracle
Original assignee: Individual
Current assignee: Procter and Gamble Co
Priority date: 2020-12-09
Filing date: 2021-12-07
Publication date: 2022-06-16
Also published as: EP4259286A1; JP2023549189A

Abstract

Treatment compositions that include pro-fragrance silicone polymers, where the pro-fragrance silicone polymers include one or more heterocyclic moieties, where the heterocyclic moieties include a residue of an aldehyde-containing perfume raw material, a ketone-containing perfume raw material, or a mixture thereof. Related premix compositions. Methods of making and using such pro-fragrance silicone polymers, related premix compositions, and treatment compositions. Related pro-fragrance silicone polymers and precursor silicone polymers.

Description

TREATMENT COMPOSITIONS WITH PRO-FRAGRANCE SILICONE POLYMERS THAT
COMPRISE HETEROCYCLIC MOIETIES
FIELD OF THE INVENTION
The present disclosure relates to treatment compositions that include pro-fragrance silicone polymers that include one or more heterocyclic moieties, where the heterocyclic moieties include a residue of an aldehyde-containing perfume raw material, a ketone-containing perfume raw material, or a mixture thereof The present disclosure also relates to related premix compositions, pro-fragrance silicone polymers, and precursor silicone polymers. The present disclosure also relates to related methods of making and using such silicone polymers, premix compositions, and treatment compositions.
BACKGROUND OF THE INVENTION
Consumer product manufacturers and consumers alike desire treatment compositions that provide freshness benefits. To address this need, neat perfume raw materials (PRMs) have been utilized as a means to deliver freshness in consumer products such as is in the case of a laundry treatment application, where the delivery of such freshness may be achieved during pre-treatment, laundry cycle, rinse cycle, tumbling cycle or combinations thereof. While such applications do yield scented fabrics, they do not exhibit sustained delivery of scents or deposit with high efficiencies. As such, there is an effort to develop a composition capable of overcoming these challenges.
Pro-fragrance compounds can be useful to manufacturers of various treatment compounds, such as consumer products like liquid fabric enhancers, detergents, or dryer sheets. A "pro-fragrance compound" is a compound which may or may not be odoriferous in itself but which, upon external stimulation (e.g. light, temperature, or moisture), produces an odor which is characteristic of one or more of its released fragrance materials. Such compounds typically release fragrance materials (i.e., perfume raw materials) upon hydrolysis of a chemical bond, which can result in a desirable release profile, for example by delaying the release of the fragrance materials and with a combined scent character that may not be readily obtained from only a neat perfume oil.

2 Various silicon-based compounds are known in the art for being useful as pro-fragrance carriers, but they typically present certain challenges. For example, silicic acid esters are known for use as base molecules for pro-fragrance materials. However, the silicic acid ester bonds are often hydrolytically unstable, resulting in premature perfume release. Amino-modified silicones are also known to be useful as the backbones of pro-fragrance materials, but such materials may form imine bonds with the perfume raw materials, thereby leading to color and/or physical instabilities.
Therefore, there is still a need for improved silicone-based pro-fragrance materials, as well as stable and effective treatment compositions and related methods that employ them.
SUMMARY OF THE INVENTION
The present disclosure relates to pro-fragrance silicone polymers. The polymers include one or more heterocyclic moieties that include the residue of a perfume raw material. For example, the pro-fragrance silicone polymer may include a silicone backbone, an organic linker group that includes a carbon atom bonded to a silicon atom of the silicone backbone, and a heterocyclic moiety bonded to the organic linker group, where the heterocyclic moiety comprising from five to seven ring members, the ring members including: a first ring member that is a nitrogen atom; a second ring member that is a carbon atom, where the second ring member is part of a residue of a perfume raw material ("PRM"), where the PRM
that formed the residue includes a moiety selected from an aldehyde moiety, a ketone moiety, and a combination thereof; a third ring member selected from the group consisting of an oxygen atom or a sulfur atom, preferably an oxygen atom, where the second ring member is directly bonded to the first ring member and to the third ring member. The present disclosure also relates to related precursor silicone polymers that are capable of forming such pro-fragrance silicone polymers.
The present disclosure also relates to treatment compositions having a treatment adjunct and a pro-fragrance silicone polymer.
The present disclosure also relates to premix compositions, where the premix may include (a) a pro-fragrance silicone polymer and optionally one or more free perfume raw materials, and/or (b) a precursor silicone polymer and a perfume raw material that comprises a moiety selected from an aldehyde moiety, a ketone moiety, or a combination thereof, where the

3 precursor silicone polymer and the perfume raw material are capable of condensing to form a pro-fragrance silicone polymer.
The present disclosure further relates to methods of making such treatment compositions and liquid premix compositions.
The present disclosure further relates to methods of treating a surface or an article with such treatment compositions, as well as surfaces or articles that include the pro-fragrance silicone polymer.
The present disclosure also relates to the use of such pro-fragrance silicone polymers as a perfuming agent.
DETAILED DESCRIPTION OF THE INVENTION
The present disclosure relates to pro-fragrance silicone polymers and certain precursor silicone polymers, as well as related premixes, treatment compositions, and methods of making and using such materials and compositions.
The pro-fragrance silicone polymers of the present disclosure comprise a heterocyclic moiety, such as an oxazolidine, that includes the residue of a perfume raw material. Such polymers may be formed by combining certain nitrogen-containing precursor silicone polymers with certain perfume raw materials, for example in a premix, and then treating an article or surface with a composition that includes the combination.
Without wishing to be bound by theory, it is believed that the heterocyclic moiety formed when a perfume raw material condenses with certain silicone precursors tend to result in improved color and chemical stability compared to pro-fragrance materials formed from known amino-modified silicones or silicic acid esters. For example, compared to imine bonds derived from such amino-modified silicones, the heterocyclic pro-fragrance materials described herein are less likely to form conjugated systems and lead to undesirable color changes. Further, it is believed that the heterocyclic moieties covalently appended to a silicone polymer (e.g.. Si-CR') result in improved chemical stability upon storage, for example compared to the silicic acid ester bonds (e.g., Si-OR'), resulting in a longer release profile and more perfume released at later touchpoints. Furthermore, greater hydrophobicity of the precursor silicone polymers and resulting pro-fragrance silicones may result in improved PRM association and/or deposition. Additionally, it is believed that the

4 perfume release profile can be tuned by the manufacturer by adjusting the polymer size and/or the substituent groups on the ring of the heterocyclic moiety. Additionally, it is believed that the heterocyclic moieties of the present disclosure are relatively stable under acidic conditions, for example a pH of from about 2 to about 4, such as those that are typical of liquid fabric softeners/conditioners.
The materials, compositions, and methods are discussed in more detail below.
As used herein, the articles "a" and "an" when used in a claim, are understood to mean one or more of what is claimed or described. As used herein, the terms "include,"
"includes," and "including" are meant to be non-limiting. The compositions of the present disclosure can comprise, consist essentially of; or consist of, the components of the present disclosure.
The terms "substantially free of" or "substantially free from" may be used herein. This means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. The indicated material may be present, if at all, at a level of less than 1%, or less than 0.1%, or less than 0.01%, or even 0%, by weight of the composition.
As used herein "consumer product" means baby care, personal care, fabric &
home care, family care, feminine care, health care, snack and/or beverage products or devices intended to be used or consumed in the form in which it is sold, and not intended for subsequent commercial manufacture or modification. Such products include but are not limited to diapers, bibs, wipes;
products for and/or methods relating to treating hair (human, dog, and/or cat), including, bleaching, coloring, dyeing, conditioning, shampooing, styling; deodorants and antiperspirants; personal cleansing; cosmetics; skin care including application of creams, lotions, and other topically applied products for consumer use; and shaving products, products for and/or methods relating to treating fabrics, hard surfaces and any other surfaces in the area of fabric and home care, including: air care, car care, dishwashing, fabric conditioning (including softening), laundry detergency, laundry and rinse additive and/or care, hard surface cleaning and/or treatment, and other cleaning for consumer or institutional use; products and/or methods relating to bath tissue, facial tissue, paper handkerchiefs, and/or paper towels; tampons, feminine napkins; products and/or methods relating to oral care including toothpastes, tooth gels, tooth rinses, denture adhesives, tooth whitening; over-the-counter health care including cough and cold remedies, pain relievers, RX
pharmaceuticals, pet health and nutrition, and water purification.
As used herein the phrase "fabric care composition" includes compositions and formulations designed for treating fabric. Such compositions include but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein.
Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation.
As used herein, "fragrance premix composition," "premix composition," and "premix" are used interchangeably, unless otherwise indicated.
As used herein, "amine content," "amine value," and "amine content values" are used interchangeably unless indicated otherwise and can be determined according to the method provided in the Test Method section. Weight percent of nitrogen can be determined from the total amine value as provided in the Test Method Section.
As used in the present disclosure, the term "polymer" includes homopolymers, i.e. obtained by polymerization of one type of monomer with appropriate end cap, as well as copolymers, i.e.
obtained by the polymerization of two or more types of monomers. It is understood that in the present invention the term "polymers" includes higher order oligomers (such as trimers, tetramers etc.). Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
All temperatures herein are in degrees Celsius ( C) unless otherwise indicated. Unless otherwise specified, all measurements herein are conducted at 20 C and under the atmospheric pressure.

In all embodiments of the present disclosure, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise.
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
Pro-Fragrance Silicone Polymer The present disclosure relates to pro-fragrance silicone polymers. Such polymers are useful in delivering a fragrance, for example to a target surface. In particular, the pro-fragrance silicone polymers of the present disclosure include a heterocyclic moiety, where the heterocyclic moiety includes a fragment of a perfume raw material. The heterocyclic moiety may be formed by a condensation reaction between, for example, an aldehyde- or ketone-containing perfume raw material and a portion of a silicone precursor that includes an alkanolamine or thiol amine moiety.
The perfume raw material is then released upon hydrolysis.
It has been found that by associating the perfume raw materials with the silicone polymer precursors in the fashion described herein, desirable benefits associated with color stability, perfume deposition, and/or perfume release profiles can be achieved.
The present disclosure relates to a pro-fragrance silicone polymer comprising a silicone backbone, an organic linker group, and a heterocyclic moiety bonded to the organic linker group.
The organic linker group comprises a carbon atom bonded to a silicon atom of the silicone backbone. As described in more detail below, the heterocyclic moiety comprises a residue of a perfume raw material.
The pro-fragrance silicone polymer comprises a silicone backbone. Typically, the silicone backbone is a siloxane backbone. By "backbone" it is meant the silicone polymer that provides the scaffolding to which the organic linker group is attached. The silicone backbone is typically formed from the precursor silicone polymer, described in more detail below.
The silicone backbone may be functionalized, for example with X groups and Y or Z groups, as described in more detail below. The silicone backbone may be linear or branched.
It may be preferred that the organic linker group and the heterocyclic moiety, together, form a pendant group that is attached to the silicone backbone. The pendant group, specifically a terminal carbon atom of the linker group, may be bonded to a silicon atom located at a terminal position of the silicone backbone; such silicon atoms are referred to herein as a "terminal silicon atom." The pendant group, specifically a terminal carbon atom of the linker group may be bonded to a silicone atom located at a non-terminal position of the silicone backbone; such silicon atoms are referred to herein as "non-terminal silicon atoms." It may be preferred for the pro-fragrance silicone polymer to comprise one or more pendant groups bonded to one or more non-terminal silicon atoms; this configuration may be preferred because it may allow for greater PRM loading opportunities, given that for many silicone polymers, there are more non-terminal silicon atoms than there are terminal silicon atoms. A pro-fragrance silicone polymer may have pendant groups bonded to terminal silicon atoms and pendant groups bonded to non-terminal silicon atoms. It may even be that one pendant group is bonded to another pendant group.
A pendant group may comprise one or more residues of a perfume raw material, for example at least two residues. At least one of these residues, e.g. a first PRM residue, is part of the heterocyclic moiety, e.g., a first heterocyclic moiety. A second PRM
residue may be part of a second heterocyclic moiety on the same pendant group. A second PRM residue may be located on the same pendant group but may not be part of a second heterocyclic moiety;
for example, a second PRM residue may be bonded to the pendant group by way of an imine bond. A
second PRM
residue may be bonded to the organic linker group. A second PRM residue may be located in a relatively terminal position on the pendant group relative to the first PRM
residue. Put another way, the second PRM residue may be located in a distal position relative to both the first PRM
residue and the silicone backbone.
The organic linker group and the heterocyclic moiety may be connected to two or more silicone backbones. The organic linker group and the heterocyclic moiety may effectively cross-link two silicone polymer fragments. In an alternative configuration, the organic linker group and the heterocyclic moiety may link two silicone polymer fragments in a linear fashion, such is the case illustrated by Synthetic Example 18, below.

The heterocyclic moiety preferably comprises from five to seven ring members.
It is understood that the heterocyclic moiety may comprise additional atoms, for example as substituents; the five to seven ring members are only those atoms that form the "ring" of the heterocyclic moiety.
Several of the ring members, namely first, second, and third ring members, have particular identities. For example, the ring members comprise a first ring member that is a nitrogen atom.
The second ring member is a carbon atom. Furthermore, the second ring members (i.e., the carbon atom) is part of a residue of a perfume raw material ("PRM", or a parent PRM), where the PRM that formed the residue comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and combinations thereof. More specifically, the carbon atom is the carbon of an aldehyde moiety or ketone moiety of the parent PRM. The heterocyclic moiety forms when a condensation reaction occurs between an amine-containing portion (for example, an alkanolamine or a thiol amine) of a silicone precursor polymer and the parent PRM. Such PRMs are discussed in more detail below. Although transient in low amounts, open-chain tautomers may be present during the formation of the described heterocycles.
The third ring member is an oxygen atom or a sulfur atom, preferably an oxygen atom. It may be preferred for the third ring member to be an oxygen atom as it is believed to have faster rates of PRM hydrolysis, higher PRM loading, improved viscosity profiles, and improved stability.
The second ring member is bonded directed to the first ring member. The second ring member is also bonded directly to the third ring member. When the third ring member is an oxygen atom, when the heterocyclic moiety has five ring members, and when the fourth and fifth ring members are carbon atoms, the heterocyclic moiety is an oxazolidine-type structure. When the third ring member is a sulfur atom, when the heterocyclic moiety has five ring members, and when the fourth and fifth ring members are carbon atoms, the heterocyclic moiety is a thiazolidine-type structure. When the third ring member is an oxygen atom, when the heterocyclic moiety has six ring members, and when the fourth, fifth, and sixth ring members are carbon atoms, the heterocyclic moiety may be an oxazinane- or an oxazine-type structure. When the third ring member is a sulfur atom, when the heterocyclic moiety has six ring members, and when the fourth, fifth, and sixth ring members are carbon atoms, the heterocyclic moiety may be a thiazinane- or a thiazine-type structure.

The general structure of an oxazolidine ring is shown below. The structure has five ring members, each labeled with a number (1-5). It is understood that in the present disclosure, such rings will be substituted, at least at the second ring member, which, as described above, is the residue of a PRM. Furthermore, such ring members will be bonded, directly or indirectly, to the organic linker group and ultimately to the silicone backbone.
NH
CO)'' The pro-fragrance silicone polymers of the present disclosure may comprise at least one radical selected from the group consisting of Formula I, Formula II, and mixtures thereof, where the radicals of Formula I and Formula II have the following structures:
(Si) ¨ X ¨ Z Formula I;
(Si) ¨ X ¨ (Z ¨ X),, ¨ (Si) Formula II;
where "(Si) ¨" represents the bond to an Si atom, where each X group is the organic linker group and is an independently selected divalent organic moiety group comprising from 2 to 24 chain atoms, where the Z group comprises the heterocyclic moiety, and where the index n in Formula II
is 1 or 2, preferably 1.
The pro-fragrance silicone polymer may have at least one radical, preferably more than one radical, from the group consisting of Formula I, Formula II, and mixtures thereof. In some cases, the pro-fragrance silicone polymer may have one radical according to Formula I, Formula II, or mixtures thereof. The molar ratio of the radicals (e.g., the -X-Z group) to silicon atoms in the pro-fragrance silicone polymer may be, on average, from about 1:1 to about 1:500, or from about 1:2 to about 1:100, or from about 1:2 to about 1:50, or from about 1:2 to about 1:20, or from about 1:2 to about 1:15, or from about 1:2 to about 1:12, or from about 1:5 to about 1:12. Relatively more radicals may be preferred so that a single pro-fragrance silicone polymer has higher loading capacity with regard to PRMs and can therefore delivery greater degrees of freshness benefits more efficiently. However, ratios that are too high may result in stability and/or cross-linking challenges.

Preferably, the at least one radical of the pro-fragrance silicone polymer has the structure of Formula I. Such radicals may correspond to the pendant groups described above and may be located at terminal silicon atoms, non-terminal silicon atoms, or combinations thereof. Radicals according to Formula I may be preferred because of commercial viability and controllable physical

5 properties in both viscosity and formulations.
The structure of Formula II indicates a linking of two polymeric silicone moieties. Such a structure may effectively cross-link two pendant silicone polymer fragments in an intra- or inter-molecular fashion (e.g., one or more X moieties are bonded to a non-terminal silicon atom).
Additionally or alternatively, such a structure may effectively link two silicone polymer fragments 10 in a linear fashion (e.g., the X moieties at the ends to of the radical are bonded to terminal silicon atoms); in such a case, the " ¨ X ¨ (Z ¨ X). ¨ " moiety may substantially be a block in the middle of a silicone backbone. Additionally, mixtures of pendant or terminal silicone polymer fragments may be cross-linked in an intra- or inter-molecular fashion. Preferably, n is equal to 1 due to ease of synthesis leading to consistent viscosity and formulation properties.
Radicals according to Formula II may be preferred for improving perfume delivery and color benefits.
As mentioned above, the "(Si) ¨" represents the covalent bond to a silicon atom of the silicon polymer. As discussed in more detail above, the silicon atom to which the X moiety is joined may be a terminal silicon atom or a non-terminal silicon atom.
A carbon atom of the X moiety is bonded to the silicon atom of the backbone, e.g., via the "(Si) ¨" bond. It is believed that configuration is more stable than if an oxygen of a linker group were to be bonded to the silicon atom. Preferably, the X group is bonded to a non-terminal silicon atom.
Each X group may independently be a divalent organic moiety having a molecular weight between about 14 and about 1000 Da, preferably between about 28 and about 495 Da, more preferably between about 42 and about 98 Da. Such molecular weights may be preferred for a variety of reasons, such as being readily commercially available and/or affordable, to maintain relatively high perfume loading by weight %, improved reactivity with the PRMs, for improved physical properties of the polymer, and/or for stability within a product or treatment composition.
As mentioned above, each X group is an organic linker group. Each X group is an independently selected divalent organic moiety group comprising from two to twenty-four chain atoms. By "chain atoms" it is meant the number of atoms directly between the silicon atom and the Z group, counted in a linear fashion. That being said, the X group may include substitutions along the chain; however, the atoms of these substitutions are not to be counted when determining the number of chain atoms. The majority of the chain atoms may be carbon atoms, although heteroatoms, preferably oxygen, may be present in the chain.
Each X group may independently comprise from two to twenty-four chain atoms, preferably from two to twelve chain atoms, more preferably from two to nine chain atoms, even more preferably from two to six chain atoms, even more preferably from three to five chain atoms.
Even more preferably, at least one of the chain atoms may be an oxygen atom.
The X group may comprise one or more oxygen atoms, preferably one oxygen atom, for example an alkoxy or an ether group. The oxygen atom may be at a non-terminal position of the X group.
The X group may be a four-carbon ether group; preferably, the X group is -CH2-CH2-CH2-0-CH2-*, preferably where the asterisk (*) is the end of the X group that is bonded to the Z
group.
The organic linker group may be independently selected from a member of the group consisting of C2-C32 substituted or unsubstituted hydrocarbon, C2-C32 substituted or unsubstituted alkoxy, C6-C32 substituted or unsubstituted aryloxy, C2-C32 substituted or unsubstituted acetoxy, C2-C32 saturated or unsaturated carbonyl, C2-C32 substituted or unsubstituted alkyl amines, C2-C32 substituted or unsubstituted hydroxy, C5-C32 substituted arenes, C2-C32 substituted or unsubstituted epoxides, C2-C32 substituted or unsubstituted episulfides, or C2-C32 substituted or unsubstituted aziridines; preferably a member independently selected from the group consisting of C2-C32 substituted or unsubstituted hydrocarbons or C2-C32 substituted or unsubstituted alkoxy;
more preferably C2-C32 substituted or unsubstituted alkoxy; most preferably C2-C32 unsubstituted alkoxy.
The organic linker group may be substituted or unsubstituted. The organic linker group may be linear or branched, preferably linear. As mentioned above, the organic linker group may have from two to twenty-four chain atoms. In such cases, if the organic linker group has, for example, more than twenty-four carbons, this indicates that the organic linker group is substituted and/or branched.
In the radicals according to Formula I and/or Formula II, the Z group comprises the heterocyclic moiety. More specifically, each Z group may be a monovalent or divalent heterocyclic moiety derivable by the removal from Formula III of a moiety selected from the group consisting of R1, one or more monovalent substituents of J, or combinations thereof, where Formula III has the following structure:
(J)m / \
Ri¨N
/G
/

Formula III
where G is selected from the group consisting of oxygen or sulfur;
where the index m is from 2 to 4, preferably m is from 2 to 3, more preferably m is 2;
where Rl is selected from H or a monovalent moiety with a molecular weight between 15 and 495 Da, more preferably R1 is selected from H or a monovalent moiety with a molecular weight between 15 and 101 Da, even more preferably Rl is H;
where each J is independently selected from the group consisting of C(R2)2, -0-, and -N(R2)-, where each R2 is independently selected from H and a monovalent moiety with a molecular weight between 14 and 990 Da, more preferably R2 is selected from H
and a monovalent moiety with a molecular weight between 14 and 186 Da, even more preferably R2 is H, with the proviso that a first unit and a second unit can optionally be taken together, where feasible, as a divalent substituent, where the first unit is a first R2 group, and where the second unit is selected from the group consisting of a second R2 group, the Rl group, and a monovalent substituent of the R1 group, preferably where the divalent substituent is selected from the group consisting of a fused ring, a spirocyclic ring, an unsaturated substituent, =N(R1), =0, and =S, where the -C(R3)(10- moiety is the residue of a perfume raw material, preferably a perfume raw material that comprises from 3 to 34 carbon atoms, where the perfume raw material from which the residue is derived comprises an aldehyde moiety, a ketone moiety, or a combination thereof, preferably where R3 is independently selected from a monovalent organic moiety, and preferably wherein is R4 is independently selected from the group consisting of hydrogen and a monovalent organic moiety, optionally, where a second moiety selected from RI, a substituent of R1, one or more monovalent substituents of J, or a combination thereof is replaced with a second link to an X group, preferably thereby forming a second ring structure. To note, in the Synthesis Examples section below, Synthetic Example 15 illustrates an example of such structures where a second ring structure is formed.
As indicated above, each Z group is derivable by the removal of a moiety from Formula III. It is important to note, however, that "derivable" in this context does not necessarily mean that the moiety is actually derived from a compound according to Formula III. In fact, it is expected that the Z moiety will rarely if ever be derived from such a compound.
Instead, the Z moiety will typically be derived from the condensation reaction of a PRM and an alkanolamine or thiol amine moiety of a silicone polymer precursor, which results in the heterocyclic moiety. Presenting Formula III as a stand-alone compound is only intended to illustrate the general formula of the Z
group, as well as the variety of ways that the Z group may be attached to the X group, in that the site of removal of a (hypothetical) moiety from Formula III indicates where the Z group is attached to the X group, typically to a terminal portion of the X group.
Put another way, one of the substituents of Formula III or even Formula IV may be a point of attachment (i.e., a covalent bond) of the Z group to the X group. More specifically, an 111 group, and/or any R2 group as described below, may be a point of attachment of attachment of Z to an X
group. Even more specifically, it may be preferred that at least one and no more than two of Rl, any R2, or mixtures thereof are a point of attachment of Z to an X group.
As described above, a second moiety, for example one selected from R', a substituent of R', one or more monovalent substituents of J, or a combination thereof, may be removed and replaced with a second link or bond to an X group. The X group may be part of the same radical or a different radical as the Z group in question. When the X group is part of the same radical, the second bond may result in a second ring structure (e.g., in addition to the heterocyclic moiety that comprises the PRM residue). In the Synthesis Examples section below, Synthetic Examples 13 and 18 illustrate examples of such structures.
As described above, the -C(R3)(R4)- moiety is the residue of a perfume raw material (PRM), where the parent PRM comprises an aldehyde moiety, a ketone moiety, or a combination thereof The "C" of the -C(R3)(R4)- moiety represents the carbon of an aldehyde or ketone moiety of the PRM, for example the aldehyde or ketone moiety that was part of the condensation reaction that resulted in the heterocyclic moiety. Thus, the parent PRM may be characterized by the formula R3-C(0)-R4. When R4 is a monovalent organic moiety, the parent PRM comprises a ketone that condenses to become part of the heterocyclic moiety. When R4 is a hydrogen, the parent PRM
comprises an aldehyde that condenses to become part of the heterocyclic moiety. Suitable perfume raw materials are discussed in more detail below.
As described above, the index in in Formula III may be from 2 to 4, preferably in may be from 2 to 3, more preferably m is 2. The lower ranges are preferred because it is believed that five-and six-membered rings, preferably five-member rings, are relatively more stable.
As described above, each J may be independently selected from the group consisting of C(R2)2, -0-, and -N(R2)-. It may be preferred that each J is independently selected from C(R2)2 for stability, for activity with perfume raw materials, and/or for release of perfume raw material reasons.
It may be preferred that each Z is a monovalent or divalent five-membered heterocyclic moiety, preferably derivable by the removal from Formula IV of a moiety selected from R1, one or more monovalent substituents of J, or combinations thereof, where Formula IV
has the following structure:

\C'G
R3 R4 Formula IV, where G, R1, R3, and R4 are as described above, preferably wherein G is oxygen, and where each J is independently C(R2)2, where R2 is as described above. In this case, index m of Formula III is 2, thereby forming a five-membered ring. Optionally, a second moiety selected from R1, a substituent of R1, one or more monovalent substituents of J, or a combination thereof is replaced with a second link to an X group, preferably thereby forming a second ring structure, more preferably this second ring structure contains a second PRM residue, where the second ring structure may be at a distal position relative to the both the first PRM
residue and the silicone backbone, or is forming a bicyclic structure with the heterocyclic moiety.

The Z group may preferably be derivable by the removal of R from Formula III
or Formula IV, meaning that the Z group is attached to the X group at the nitrogen atom shown in Formula IIT
or Formula IV.
The Z group may be preferably derivable by the removal of one or more monovalent 5 substituents of J from Formula III or Formula IV, preferably where J is -C(R2)2-, and one or more of the R2 groups are removed, meaning that the Z group is attached to the X
group at the location where the removed R2 group would have been. In such cases, it may be preferred that IV is H.
Each Z group may be a monovalent or divalent heterocyclic moiety according to Formula III, wherein formula III has the following structure:
)m / \
/G
/

Formula III, 10 wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen; wherein the index m is from 2 to 4, preferably m is from 2 to 3, more preferably m is 2; wherein IV is selected from H, a monovalent moiety with a molecular weight of from 15 to 495 Da, or a point of attachment of Z to an X group, preferably wherein 1V is H or a point of attachment of Z to an X group, wherein when Rl is present as the monovalent moiety, the monovalent moiety is 15 preferably a substituted or unsubstituted C i-C35 alkyl group, more preferably a monovalent moiety with a molecular weight of from 15 to 101 Da, even more preferably a substituted or unsubstituted C i-C8 alkyl; wherein each J is independently selected from the group consisting of C(R2)2, -0-, -N(R2)-, wherein each R2 is independently selected from H, a monovalent moiety with a molecular weight of from 14 to 990 Da, or a point of attachment of Z to an X group, wherein when R2 is present as the monovalent moiety, the monovalent moiety is preferably a substituted or unsubstituted, saturated or unsaturated C1-C70 alkyl, more preferably a monovalent moiety with a molecular weight of from 14 to 186 Da, even more preferably a substituted or unsubstituted, saturated or unsaturated Ci to C12 alkyl, preferably R2 is H or a point of attachment of Z to an X group; with the proviso that a first unit and a second unit can optionally be taken together, where feasible, as a divalent substituent, where the first unit is a first R2 group, and where the second unit is selected from the group consisting of a second R2 group, the RI group, if) and a monovalent substituent of the R1 group, preferably where the divalent substituent is selected from the group consisting of a fused ring, a spirocyclic ring, an unsaturated substituent, =N(R1), =0, and =S; wherein the -C(R3)(R4)- moiety is the residue of a perfume raw material (PRM), preferably a PRIM that comprises from 3 to 34 carbon atoms, wherein the perfume raw material from which the residue is derived comprises an aldehyde moiety, a ketone moiety, or a combination thereof, preferably wherein R3 is independently selected from a monovalent organic moiety, and preferably wherein is R4 is independently selected from the group consisting of hydrogen and a monovalent organic moiety, provided that at least one and no more than two of R1, any R2, or mixtures thereof are a point of attachment of Z to an X group.
It may be preferred that each Z is a monovalent or divalent five-membered heterocyclic moiety according to Formula IV, wherein formula IV has the following structure:
Ri-N
\C'G

Formula IV, wherein G, R3, and le are as described above, preferably wherein G is oxygen; and wherein each J is independently C(R2)2, wherein R2 is as described above.
It may be preferred that two of R1, any R2, or a combination thereof are points of attachment of Z to an X group, preferably forming a second ring structure.
It may be preferred that each Z is a monovalent or divalent heterocyclic moiety according to Formula III or Formula IV, preferably a five-membered heterocyclic moiety, wherein at least one R2 is a point of attachment of Z to an X group, preferably wherein R1 is H.
The pro-fragrance silicone polymers of the present disclosure may have a structure according to Formula V, shown below:
p [R5R6R7Si01/2](q+2r+2) [R8R9SiO2/2] LK SiO3/2L [S104/2]r Formula V, where: q is an integer from 0 to 150; p is an integer from 0 to 1500; r is an integer from 0 to 150;
where q+p+r equals an integer greater than or equal to 1; where each of R5, R6, R7, R8, R9 and R1 moiety is independently selected from the group consisting of H, OH, a monovalent organic moiety, a radical according to Formula 1, or a radical according to Formula IL
where at least one of the R5-R1 moieties is a radical according to Formula I or a radical according to Formula 11, preferably a radical according to Formula I.
When any of R5, R6, or R7 are radicals according to Formula I or Formula II, the radical is attached to a terminal silicon atom. When any of Rs, R9, or Rm are radicals according to Formula I or Formula II, the radical is attached to a non-terminal silicon atom.
As indicated above, each of R5, R6, R7, le, le and Rl moiety may be independently selected from the group consisting of H, OH, a monovalent organic moiety, a radical according to Formula I, or a radical according to Formula II. The monovalent organic moieties, if present, may be independently selected from Ci-C32 alkyl, C2-C32 alkenyl, C2-C32 alkynyl, Ci-C32 substituted alkyl, C6-C32 aryl, C5-C32 substituted aryl, C6-C32 alkylaryl, C6-C32 substituted alkylaryl, Ci-C32 alkoxy, C5-C32 aryloxy, C2-C32 acetoxy, Ci-C32 carbonyl, Ci-C32 carboxamide, Ci-C32 alky amine, Ci-C32 thiol amine, or Ci-C32 alkanolamine.
Perfume Raw Materials Certain perfume raw materials may be combined with the silicone polymer precursor, for example to form the pro-fragrance silicone polymers of the present disclosure.
As described above, the pro-fragrance silicone polymers may comprise a heterocyclic moiety, where the heterocyclic moiety comprises, among other things, a residue of a perfume raw material.
This section further describes perfume raw materials (and related residues thereof) that are suitable for incorporation into such pro-fragrance silicone polymers.
The term "perfume raw material" (or "PRM") as used herein refers to compounds having a molecular weight of at least about 100 g/mol and which are useful in imparting an odor, fragrance, essence, or scent, either alone or with other perfume raw materials. Typical PRMs comprise inter alia alcohols, ketones, aldehydes, esters, ethers, nitrites, and alkenes, such as terpene. A listing of common PRMs can be found in various reference sources, for example, "Perfume and Flavor Chemicals", Vols. land II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology", Miller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994).
The perfume raw materials that react with the silicone precursor may comprise a moiety selected from an aldehyde moiety, a ketone moiety, or combinations thereof It is believed that PRMs having one or more of these moieties are able to effectively form the heterocyclic moieties in combination with the silicone polymer precursors described herein. Further, such PRMs in combination with the silicone precursors may result in effective release and/or longevity profiles.
This is particularly advantageous given that PRMs having such moieties are common and desirable when formulating consumer-relevant olfactory experiences. Preferred PRMs may include an aldehyde moiety or a ketone moiety that is a unsaturated at the a,-position.
As mentioned above, the pro-fragrance silicone polymer, specifically the heterocyclic moiety, may include a residue of a perfume raw material that comprises an aldehyde moiety.
Perfume raw materials that comprise an aldehyde moiety are provided below in Table A. It is believed that the materials provided in Table A are illustrative (but non-limiting) examples of PRMs that are suitable for use according to the present disclosure.
Table A. Aldehyde-containing perfume raw materials.
Number Registry Name Trade Name 1 3-Cyclohexene-1-carboxaldehyde, dimethyl- Ligustral 2 3-Cyclohexene-1-carboxaldehyde, 2,4,6- Isocyclocitral trimethyl-3 Cyclohexanemethanol, .alpha.,3,3-trimethyl-, Aphermate formate 4 3-(4-tert-butylphenyl)butanal; pt-bucinal; 3-(4- Lilial tert-butylphenyl)butanal 5 2-methylundecanal Methyl Nonyl Acetaldehyde

6 1-methyl-3-(4-methylpent-3-enyl)cyclohex-3-Precyclemone B
ene-l-carbaldehyde; myrmac aldehyde

7 Benzenepropanal, 3-(4-ethylpheny1)-2,2- Floralozone dimethylpropanal

8 2,4-dimethylcyclohex-3-ene-1-carbaldehyde Ligustral/Triplal

9 Decanal Decyl Aldehyde

10 10-Undecen-1-al ; Undecenoic aldehyde; n- Undecylenic aldehyde;
Undecenoic aldehyde; Hendecen-10-al; Aldehyde C-11, unsaturated;Aldehyde C-11 undecylenic;

11 8-,9 and 10-Undecenal, mixture of isomers Intreleven aldehyde

12 Benzenepropanal, .alpha.-methyl-4-(1- Cymal methylethyl)-

13 2,6,10-trimethylundec-9-enal Adoxal; Farenal

14 4-(octahydro-4,7-methano-5H-inden-5- Dupical ylidene)butanal 3-Ethoxy-4-hydroxybenzaldehyde Ethyl vanillin 16 tricyclo[5.2.1.02,6]decane-3-carbaldehyde Vertral 17 4,7-Methano-1H-indene-2-carboxaldehyde, Scentenale octahydro-5-methoxy-; 6-Methoxy dicyclopentadiene carboxaldehyde; 8-Methoxytricyclo(5.2.2.1)decane-4-carboxaldehyde; Octahydro-5-methoxy-4,7-methano-1H-indene-2-carboxaldehyde;
18 4-Hydroxy-3-methoxybenzaldehyde Vanillin 19 Trans-4-decenal Decenal-4-trans 20 a-hexyl-; a-n-Hexyl-f3-phenylacrolein; 2- a-Hexylcinnamaldehyde; a-Hexy1-3-pheny1-2-propenal; 2-Hexy1-3-phenyl- Hexylcinnamic aldehyde; Hexyl propenal; (2Z)-2-Hexy1-3-phenyl-2-propenal; cinnamic aldehyde;
Hexy1-3-phenyl-propenal; n-Hexyl Hexylcinnamaldehyde;
cinnamaldehyde; (2E)-2-Benzylideneoctanal; 2- Cinnamaldehyde, [(E)-Benzylidene]octanal 21 4-Dodecenal Tangerinal DIPG

22 3-Cyclohexene-1-propanal,beta,4-dimethyl- Liminale 23 trans-2-Dodecenal Mandarine aldehyde 10% C1TR

24 4,8-Dimethy1-4,9-decadienal Floral Super 25 Hydroxymyrac aldehyde; 4-(4-Hydroxy-4- Lyral methyl-penty1)-3-cyclohexen-1-carboxyaldehyde; Lyral ; Kovanol 26 2-Hexenal, (E)- 2-Hexenal 27 Benzaldehyde Benzaldehyde 28 Benzeneacetaldehyde Phenyl Acetaldehyde 29 Benzeneacetaldehyde, .alpha.-methyl- Hydratropic Aldehyde 30 3-Cyclohexene-1-carboxaldehyde, 3,5- Cyclal C, dimethyl-31 Benzaldehyde, 4-methoxy- Anisic Aldehyde 32 Octanal, 7-hydroxy-3,7-dimethyl- Hydroxycitronellal 33 3-Cyclohexene-1-carboxaldehyde, 3,6- Cyclovertal dimethyl-34 Octanal, 7-methoxy-3,7-dimethyl- Methoxycitronellal Pq 35 Benzenepropanal, beta.-methyl-; 3- Trifemal phenylbutanal 36 4,7-Methano-1H-indenecarboxaldehyde, Formyltricyclodecan octahydro-37 Octanal Octyl Aldehyde 38 5-Heptenal, 2,6-dimethyl- Melonal 39 Octanal, 3,7-dimethyl- Dihydrocitronellal 40 2-Nonenal 2 Nonen-l-al 41 6-Octenal, 3,7-dimethyl- Citronellal 42 2-Decenal 2 Decene-l-al 43 2,6-Octadienal, 3,7-dimethyl- Citral 44 Undecenal Iso C-11 Aldehyde 45 Undecanal Undecyl Aldehyde 46 2-Undecenal 2-Undecene-1-Al 47 Benzaldehyde, 4-(1-methylethyl)- Cuminic Aldehyde 48 Decanal, 2-methyl- Methyl Octyl Acetaldehyde 49 Benzenepropanal, 4-(1,1-dimethylethyl)- Bourgeonal 50 2-Dodecenal 2 Dodecene-l-al 51 Benzenepropanal, .beta.-methyl-3-(1- Florhydral methylethyl)-52 1,3-Benzodioxole-5-carboxaldehyde Heliotropin 53 3-Cyclohexene-1-carboxaldehyde, 1-methyl-4- Vernaldehyde (4-methylpenty1)-54 Benzenepropanal, 4-methoxy-.alpha.-methyl- Canthoxal 55 Cyclohexenebutanal, .alpha.,2,2,6-tetramethyl- Cetonal 56 Dodecanal Laurie Aldehyde 57 5,9-Undecadienal, 2,6,10-trimethyl- Oncidal 58 Bicyclo[2.2.2]oct-5-ene-2-carboxaldehyde, 6- Maceal methy1-8-(1-methylethyl)-59 2-methyl-3-[4-(2- cyclamen homoaldehyde methylpropyl)phenyl]propanal 60 6-methoxy-2,6-dimethyloctanal calypsone 61 4-propan-2-ylbenzaldehyde Cuminic Aldehyde 62 3,6-dimethylcyclohex-3-ene-1-carbaldehyde VERTOLIFF
63 2-methyl-3-(4-methylphenyl)propanal Jasmorangee;
satinaldehyde 64 3-phenylprop-2-enal Cinnamic Aldehyde The perfume raw material that formed the PRM residue of the heterocyclic moiety may be selected from the group consisting of the aldehyde-containing PRMs of Table A, above. The PRM
that formed the PRM residue of the heterocyclic moiety may comprise an aldehyde moiety and preferably be selected from the group consisting of: methyl nonyl acetaldehyde: benzaldehyde;

floralozone; isocyclocitral; triplal (ligustral); precylcemone B; lilial;
decyl aldehyde; undecylenic aldehyde; cyclamen homoaldehyde; cyclamen aldehyde; dupical; oncidal; adoxal;
melonal;
calypsone; anisic aldehyde; heliotropin; cuminic aldehyde; scentenal; 3,6-dimethylcyclohex-3-ene-1-carbaldehyde; satinaldehyde; canthoxal; vanillin; ethyl vanillin;
cinnamic aldehyde; and mixtures thereof.
I 0 As mentioned above, the pro-fragrance silicone polymer, specifically the heterocyclic moiety, may include a residue of a perfume raw material that comprises a ketone moiety. Perfume raw materials that comprise a ketone moiety are provided below in Table B. It is believed that the materials provided in Table B are illustrative (but non-limiting) examples of PRMs that are suitable for use according to the present disclosure.

Table B. Ketone-containing perfume raw materials.
Number Registry Name Trade Name 1 2-Buten-1-one, 1-(2,6,6-trirnethy1-3- delta-Damascone cyclohexen-1 -y1)-2 (1-(2,6,6-Trimethy1-2-cyclohexen-l-y1)-2- alpha-Damascone buten-l-one); 2-Buten-1-one, 142,6,6-trimethy1-2-cyclohexen-l-y1)-, (E)-3 (1-(2,6,6-Trimethyl-1-cyclohexen-l-y1)-2- beta-Damascone buten-1 -one); 2-Buten-1-one, 1-(2,6,6-trimethyl-1-cyclohexen-l-y1)-, (E)-4 2-Buten-1-one, 1-(2,6,6-trimethy1-1,3- Damascenone cyclohexadien-l-y1)-1,1,2,3,3-pentamethy1-2,5,6,7-tetrahydroinden- Cashmeran 4-one 6 1-(5,5-dimethy1-1-cyclohexenyl)pent-4-en-1-Neobutenone Alpha one 7 1-(5,5-dimethy1-1-cyclohexenyl)pent-4-en-1-Galbascone; Dynascone one 8 1-naphthalen-2-ylethanone Methyl Beta-Naphthyl Ketone 9 2-(2-(4-Methy1-3-cyclohexen-1- Nectaryl yl)propyl)cyclo-pentanone 2-Hexy1-2-cyclopenten-1-one (main Isojasmone B 11 component) 11 Methyl 2,6,10-Trimethy1-2,5,9- Trimofix "0"
cyclododecatrien-l-yl ketone;
12 a-Isomethyl ionone; 5-(2,6,6-Trimethy1-2- Methyl ionone; Methyl Ionone cyclohexen-1 -y1)-3 -methyl-3 -buten-2-one; Alpha Iso; Methyl Ionone Gamma; Isoraldeine 70;
Isoraldeine 95; Gamma Methylionone 600 UC; Alpha Daphnone; Iraldeine gamma;
gamma Methyl Ionone Pure;
gamma Methyl Ionone A;
Gamma Methyl Ionone Coeur 13 2-Heptylcyclopentanone; Fleuramone;
Projasmon 14 3-(Hydroxymethyl)nonan-2-one (and isomer) Methyl lavender ketone 2-Cyclohexen-1-one, 2-methy1-5-(1- Laevo Carvone methyletheny1)-, (R)-16 Bicyclo[2.2.1]heptan-2-one, 1,7,7-trimethyl-, Camphor Gum (1R)-17 2-Heptanone Methyl Amyl Ketone 18 3-Octanone Ethyl Amyl Ketone 19 2-Octanone Methyl Hexyl Ketone 5-Hepten-2-one, 6-methyl- Methyl Heptenone 21 Ethanone, 1-(4-methylpheny1)- Para Methyl Acetophenone 22 2-Butanone, 4-phenyl- Benzyl Acetone 23 1,4-Methanonaphthalen-5(1H)-one, Tamisone 4,4a,6,7,8,8a-hexahydro-24 2H-1-Benzopyran-2-one, 3,4-dihydro- Dihydrocoumarin 25 Cyclohexanone, 5-methyl-2-(1-methylethyl)-, Iso Menthone cis-26 2H-Pyran-2-one, 6-butyltetrahydro- Nonalactone 27 3-Hepten-2-one, 3,4,5,6,6-pentamethyl- Koavone 28 Cyclopentanone, 3-methyl-2-pentyl- Jasmylone 29 3-Nonanone Ethyl Hexyl Ketone 30 Ethanone, 1-(3,3-dimethylcyclohexyl)- Herbac 31 3-Heptanone, 5-methyl-, oxime Stemone 32 Cyclohexanone, 2-(1-methylpropy1)- 2-Sec-Butyl Cyclo Hexanone 33 Cyclopentanone, 2-pentyl- Delphone 34 2-Cyclopenten-1-one, 3-methy1-2-pentyl-Dihydrojasmone 35 Cyclohexanone, 5-methyl-2-(1-methylethyl)-, Menthone Racemic trans-36 Cyclohexanone, 4-(1,1-dimethylpropy1)- Orivone 37 2-Undecanone Methyl Nonyl Ketone 38 1-Decanol Rhodalione 39 2-Cyclohexen-1-one, 3-methyl-5-propyl- Livescone 40 2-Cyclopenten-1-one, 2-methyl-3-(2-penteny1)- Iso Jasmone 41 Ionone Ionone Ab 42 3-Buten-2-one, 4-(2,6,6-trimethy1-2- Ionone Alpha cyclohexen-1 -y1)-, (E)-43 3-Buten-2-one, 4-(2,6,6-trimethy1-1- Ionone Beta cyclohexen-1 -y1)-44 2-Buten-1-one, 1-(2,4,4-trimethy1-2- Isodamascone N
cyclohexen-1 -y1)-, (E)-45 2H-1-Benzopyran-2-one Coumarin 46 Cyclopentanone, 2-heptyl- Fleuramone 47 3-Decanone, 1-hydroxy- Methyl Lavender Ketone 48 1-Propanone, 1-[2-methy1-5-(1-methylethyl)-2- Nerone cyclohexen-1 -y1]-49 9-Undecen-2-one, 6,10-dimethyl- Tetra Hydro Psuedo Ionone 50 1-phenylethanone Acetophenone 51 2-butan-2-ylcyclohexan-1-one Freskomenthe 52 Ethanone, 1-(3-methy1-2-benzofurany1)- nerolione 53 4-(4-methoxyphenyl)butan-2-one Anisyl Acetone The perfume raw material that formed the PRM residue of the heterocyclic moiety may be selected from the group consisting of the ketone-containing PRMs of Table B, above. The PRM
that formed the PRM residue of the heterocyclic moiety may comprise a ketone moiety and may preferably be selected from the group consisting of: nerolione; 4-(4-methoxyphenyl)butan-2-one;

1-naphthalen-2-ylethanone; nectaryl; trimotix 0; fleuramone; delta-damascone;
beta-damascone;
alpha-damascone; methyl ionone; 2-hexylcyclopent-2-en- 1 -one; galbascone; and mixtures thereof.
The pro-fragrance silicone polymers of the present disclosure may be used in combination with other perfume raw materials, even PRMs that do not contain an aldehyde or ketone moiety.
Other perfume raw materials, such as those that do not contain an aldehyde moiety or a ketone moiety, may also be mixed with the silicone precursor, as it is believed that the hydrophobic silicone droplets may facilitate deposition of certain PMRs, even if a condensation reaction does not occur. Additionally or alternatively, it is possible that the PRMs in question may react with other portions of the silicone precursor, even if the reaction does not result in a heterocyclic moiety as described herein. Additionally or alternatively, the PRMs may react with other compounds, such as low-molecular-weight amines, that may in turn react with the silicone precursor. It may even be that a materials supplier may wish to provide reacted PRMs and unreacted PRMs in the same silicone emulsion, for example to save on packaging, shipping, or storage costs. Additionally or alternatively, other PRMs may be provided as neat or free oils to the premix composition and/or 1.5 the treatment compositions according to the present disclosure, for example to provide a more well-rounded olfactory experience.
Other perfume raw materials are provided below in Table C. It is believed that the materials provided in Table C are illustrative (but non-limiting) examples of PRMs that are suitable for use according to the present disclosure. For example, these "other" PRMs may be co-formulated with the pro-fragrance silicone polymers of the present disclosure, for example by being added as neat or encapsulated perfume. It may even be that the pro-fragrance silicone polymers can further react/condense with one or more other perfumes, even if a heterocyclic moiety is not formed in the process.
Table C. Other perfume raw materials.
Number Registry Name Trade Name 1 Ethyl 2 Methyl Pentanoate Manzanate 2 3,7,11-Trim ethy1-2,6,10-dodecatrien-12-ol ; Farnesol 2,6,10-Dodecatrien-1-ol, 3,7,11-trimethyl-;
Farnesol; Farnesyl alcohol; 3,7,11-Trimethy1-2,6,10-dodecatrien- 1 -ol; 3,7,11-Trimethy1-2,6,10-dodecatrienol; Trimethy1-2,6,10-dodecatriene-l-ol; (2E,6E)-3,7,11-Trimethy1-2,6,10-dodecatrien-1-ol; a-Farnesol; alpha-Farnesol; 3,7,11-Trimethyldodeca-2,6,10-trien-l-ol; 3,7, 11-Trimethy1-2,6,10-dodecatrien-l-ol (farnesol); (E)-alpha-Farnesol 3 (1-Methy1-2-(1,2,2 -trimethylbicyclo [3 .1.01-Javanol hex-3-ylmethyl)cyclopropyl)methanol (Mixture of diastereoisomers) 4 2-Methy1-3-{(1,7,7- Bornafix trimethylbicyclo {2.2.1}hept-2-ypoxyl exo-l-propanol and isomers 2-Methyl-4-(2,2,3-trimethylcyclopent-3-en-1- Brahmanol yl)butan-l-ol; 2-Methy1-4-(2,2,3-trimethy1-3-cyclopenten-1-y1)-butan-1-01 6 2-Ethyl-4-(2,2,3-trimethyl-3-eyelo-penten-1- Baedanol Baedanol ;
y1)-2-buten-1-ol; 2-Ethyl-4-(2,2,3-trimethy1-3- Sandranol;
Bangalol; Sandolen ;
cyclopenten-l-y1)-2-buten-1-ol; B-Ethyl-2,2,3- Balinol; Laevo Trisandol;
trimethy1-3-Cyclopentene-1-but-2-enol; Ethyl Levosandol;
Trimethylcyclopentene Butenol 7 Cyclohexanemethanol, 4-(1-methylethyl)-, cis-; Mayol 4-Isopropylcyclohexanemethanol;
8 2-Methy1-5-phenylpentan-1-ol Rosaphen 9 3-Methy1-5-phenylpentanol; 3-Methyl-5- Phenoxanolg;
Mefrosol; Phenyl phenyl-l-pentanol; hexanol 9-decen-1-ol; 9-Decenol; Rosalva; Trepanol 11 2-Methyl-4-(2,2,3-trimethy1-3-cyclopenten-1-Hindinol; Sandalmysore core;
y1)-2-buten-1-o1;; 2-Buten-1-ol, 2-methyl-4- Santalaire;
Madranol;
(2,2,3-trimethy1-3-cyclopenten-1-y1)-; 2-Buten- Santaliffrm 1-o1,2-methy1-4-(2,2,3-trimethy1-3-cyclopenten-1 -y1)-12 3-Cyclohexene-1-propanol gamma 4-dimethyl-Cyclomethylene citronellol 13 2,2-Dimethy1-3-(3-methylphenyl)propan-1-ol Majantol 14 3,7-Dimethy1-6-octen-1-01, (-)-Citronellol;
Citronellol Rhodinol (2E,6Z)-nona-2,6-dien-1-ol 2,6-Nonadienol 16 2-[(1,7,7-Trimethylbicyclo[2.2.1]hcpt-2- Ccdanol yl)oxy1-ethanol 17 2,4,6-Trimethy1-3-cyclohexene-1-methanol Isocyclogeraniol 18 3,7-Dimethyl-trans-2,6-octadien-1-ol; 3,7- Geraniol Dimethy1-2,6-octadien-1-01 (isomers); trans-Geraniol; Guaniol; Lemonol; trans-3,7-Dimethy1-2,6-octadien-1-01; Geraniol alcohol;
Geraniol extra; Geranyl alcohol; 2,6-Dimethyl-trans-2,6-octadien-8-ol; 2,6-Octadien-1-ol, 3,7-dimethyl-, trans-; 3,7-Dimethyl-trans-2,6-octadien-1-ol; (E)-3,7-Dimethy1-2,6-octadien-1-ol; Meranol; trans-3,7-Dimethyl octa-2,6-di en-l-ol ; (2E)-3,7-Dimethy1-2,6-octadien-1-01 ;
Nerol; Neryl alcohol; trans-3,7-Dimethy1-2,6-octadien-1-ol (geraniol); t-Geraniol; (E)-Geraniol; (E)-3,7-Dimethy1-2,6-octadien-1-01;
Geraniol (E) 19 Dihydrocinnamic alcohol; 3-Phenylpropanol; 3-Phenylpropyl alcohol Benzenepropanol; 1-Propanol, 3-phenyl-; y-Phenylpropanol; 7-Pheny1propy1 alcohol; (3-Hydroxypropyl)benzene; Hydrocinnamic alcohol; Hydrocinnamyl alcohol; 3-Phenyl-n-propanol; 3-Phenyl-1-propanol; 3-Phenylpropyl alcohol; 3-Benzenepropanol; Phenylpropyl alcohol; 1-Hydroxy-3-phenylpropane; 3-Phenylpropan-1-01; Phenylpropylic alcohol 20 Cinnamic alcohol; 3-Pheny1-2-propen-1-ol; Cinnamic alcohol Cinnamyl alcohol; 7-Phenylally1 alcohol;
Pheny1-2-propen-1-01; Styrone; Styryl carbinol;
3-Phenylally1 alcohol; 1-Phenyl-1-propen-3-01;
3-Phenyl-2-propen-l-ol ; 3 -Phenyl-2-propenol ;
Alkohol skoricovy; 3-Feny1-2-propen-1-01;
Peruvin; Phenyl-2-propenol; Phenylallyl alcohol; (2E)-3-Pheny1-2-propen-1-ol; 3-phenylprop-2-en-1-01; 2-Propen-1-ol, 3-phenyl-21 2-Hexen-1-ol, (E)-; trans-2-Hexen-1-01; trans- trans-2-Hexenol 2-Hexenol; 2-Hexenol; 2-Hexen-1-ol, trans-;
(2E)-2-Hexen-1-ol; (E)-2-Hexenol; (E)-Hex-2-en-l-ol; (E)-Hex-2-enol; (E)-2-Hexene-1-ol ;
Hex-2(E)-enol; t-2-Hexen-1-ol; 2-(E)-hexenol;
trans-Hex-2-en-1-ol 22 4-(5,5,6-Trimethylbicyclo[2.2.1]hept-2- Sandela yl)cyclohexan-l-ol (and isomers, 85% solution in IPM) 23 1-Naphthaleno1,1,2,3,4,4a,5,8,8a-octahydro- Octalynol 2,2,6,8-tetramethyl-24 3-Methyl-5-(2,2,3-trimethy1-3-cyclopenten-1- Ebanol y1)-4-penten-2-ol;
25 4-Methyl-3-decen-5-ol Undecavertol 26 4-Penten-2-ol, 3,3-dimethyl-5-(2,2,3-trimethyl- Nirvanol 974650;
3-cyclopenten-l-y1)- ; Polysantolm 974656 27 3-Methyl-4-phenylbutan-2-ol Muguesia 28 2-Methoxy-4-allylphenol Eugenol 29 Cyclohexanepropanol, 2,2,6-trimethyl-alpha-Norlimbanol 967412;
propyl-; 1-(2,2,6-Trimethylcyclohexyl)hexan- Timberol8;
3-ol 5-Propeny1-2-ethoxyphenol; Propenyl guaethol; Vanitrope 31 1-(4-Isopropy1-cyclohexyl) ethanol; 1-(4- Mugetanol Isopropylcyclohexyl)-ethanol 32 2-Pentylcyclopentan-1-ol; 2- Cyclopentol HC

Pentylcyclopentanol 33 3,7,11-Trimethy1-1,6,10-dodecatrien-3-01 Nerolidol 34 Cedrol Crude Cedrol 3,7-Dimethy1-7-hydroxyoctan-1-al dimethyl Hydroxycitronellal dimethyl acetal acetal 36 4-Methyl-2-(2-methylpropyl)tetrahydro-2H- Florosa pyran-4-ol; Florol 966458 37 2,5,5-Trimethyl-octahydronaphthalen-2-ol; Ambrinol 20-T
38 2,5,5-Trimethy1-1,2,3,4,4a,5,6,7-octahydro-2-Ambrinol; Ambrinol S
naphthalenol;
39 4-Methyl- 14 sopropy1-3-cyclohexen-1-01 Terpinen-4-ol 40 3,7-Dimethyl-1,6-nonadien-3-ol (cis & trans) Ethyl linalool 41 1-Methyl-3-(2-methylpropyl)cyclohexanol Rossitol 42 4-Phenyl-2-methyl-2-butanol a,a-Dimethylphenylethylcarbinol 43 3,7-Dimethyloctan-1,7-diol Hydroxyol 44 1-Methyl-4-isopropylcyclohexane-8-ol Dihydro terpineol 45 3,7-Dimethyl-1,6-octadiene-3-ol Linalool 46 3,7-Dimethyl-4,6-octadien-3-ol Allo-Ocimenol;
Muguol 47 2-(4-Methyl-cyclohex-3-eny1)-propan-2-ol; p- alpha Terpineol, LindenolTM
Menthan-8-ol 48 1-Phenyl-2-methyl-2-propanol; a,a- 2-methyl-1-phenylpropan-2-ol Dimethylbenzyl carbinol; benzeneethanol, a,a-dimethyl-49 Cyclohexanepropano1,2,2-dimethyl- Coranol 928130 50 2,6-Dimethyl-7-octen-2-ol; 2-Methyl-6-Dihydromyrcenol, Dihydro methyleneoct-7-en-2-ol, dihydro derivative; 7- Myrcenol Octen-2-ol, 2,6-dimethyl-; 2,6-Dimethy1-7-octen-2-ol; 3,7-Dimethyl-1-octen-7-ol; 2,6-Dimethyl-oct-7-en-2-ol; Mircenol, 6,10-dihydro 51 3,7-Dimethyloctan-3-ol Tetrahydrolinalool 52 2,6-Dimethyl-2-octanol Tetrahydro myrcenol 53 2,6-Dimethyl-2-heptanol Dimetol , Freesiol , Lolitol 54 2-Hexen-1-ol 2-Hexen-1-ol 55 3-Hexen-1-ol Beta Gamma Hexenol 56 Ethanol, 2,2'-oxybis- Calone 161 57 Benzoic acid, 2-amino-, methyl ester Methyl Anthranilate 58 2H-Pyran, 3,6-dihydro-4-methyl-2-(2-methyl- Nerol Oxide 1-propeny1)-59 Benzeneethanol, .beta.-methyl- Hydratropic Alcohol 60 Benzeneethanol, .alpha.,.alpha.-dimethyl- Dimethyl Benzyl Carbinol 61 Benzoic acid, 2-(methylamino)-, methyl ester Dimethyl Anthranilate 62 1-Heptanol Heptyl Alcohol 63 Ethanol, 2-(2-methoxyethoxy)- Veramoss Sps 64 Cyclohexaneethanol Cyclohexyl Ethyl Alcohol 65 3-Octen-1-ol, (Z)- Octenol Dix 66 Ethanone, 1-(4-methylpheny1)- Para Methyl Acetophenone 67 Linalool oxide Linalool Oxide 68 Benzenepropanol Phenyl Propyl Alcohol 69 Ethanol, 2-phenoxy- Phenoxyethanol 70 1H-Indole Ind le 71 1,3-Dioxolane, 2-(phenylmethyl)- Ethylene Glycol Acetal/Phenyl Acetaldehy 72 Cyclohexanol, 1-methyl-4-(1-methylethyl)-Dihydroterpineol 73 3,5-Octadien-2-ol, 2,6-dimethyl-, (?,Z)- Muguol 74 3-Cyclohexen-1-01, 4-methyl- 1-(1- Terpinenol methylethyl)-75 Bicyclo[2.2.1]heptan-2-ol, 1,3,3-trimethyl- Fenchyl Alcohol 76 Cyclohexanol, 2-(1,1-dimethylethyl)-, cis- Verdol 77 Bicyclo[2.2.1]heptan-2-ol, 1,7,7-trimethyl-, Borneo!
Crystals (1S-endo)-78 Cyclohexanol, 5-methyl-2-(1-methylethyl)- Menthol 79 Cyclohexanol, 2-(1,1-dimethylethyl)-, acetate Verdox 80 3-Octanol Octano1-3 81 2-Heptanol, 2,6-dimethyl- Dimethy1-2, 6-Heptan-2-ol 82 1-Octanol Octyl Alcohol 83 3-Octanol, 3,7-dimethyl- Linacsol 84 Isononanol 'so Nonyl Alcohol 85 1-Nonanol Nonyl Alcohol 86 1-Octanol, 3,7-dimethyl- Dimethyl Octanol 87 6-Octen-1-ol, 3,7-dimethyl-, (S)- Baranol 88 Cyclohexanol, 3,3,5-trimethyl-, cis- Trim ethylcyclohexanol 89 1-Hexanol, 5 -methyl-2-(1-methylethyl)-, (R)-Tetrahydro Lavandulol 90 Cyclohexanol, 4-(1-methylethyl)- Roselea 91 7-Octen-2-ol, 2,6-dimethyl-, formate Dimyrcetol 92 5,7-Octadien-2-ol, 2,6-dimethyl- Ocimenol 93 2H-Pyran, 6-butyl-3,6-dihydro-2,4-dimethyl- Gyrane 94 Cyclohexanol, 4-(1,1-dimethylethyl)- Patchon 95 Cyclohexanol, 5-methyl-2-(1-methylethyl)-, Menthol Natural [1R- (1.alpha.,2.beta.,5.alpha.)]-96 2-Nonanol, 6,8-dimethyl- Nonadyl 97 Phenol, 4-(1,1-dimethylethyl)- Para Tertiary Butyl Phenol 98 Cyclohexanol, 5-methyl-2-(1-methyletheny1)-, Iso Pulegol [1R-(1.alpha.,2.beta.,5.alpha.)]-99 1-Decanol Rhodalione 100 Phenol, 2-methy1-5-(1-methylethyl)- Carvacrol 101 2-Naphthalenol, decahydro- Trans Deca Hydro Beta Naphthol 102 Phenol, 5-methy1-2-(1-methylethyl)- Thymol Nf 103 Phenol, 2-methoxy-4-propyl- Dihydro Eugenol 104 Benzene, 1,2-dimethoxy-4-(2-propeny1)- Methyl Eugenol 105 Ethanol, 2- [(1, 7,7 -trimethylb icyclo [2 .2 .1]h ept-Arbanol 2-yl)oxy]-, exo-106 Phenol, 4-ehloro-3,5-dimethyl- 4-Chloro 3,5 Xylenol The perfumes raw materials in this specification, including the perfume raw materials listed above, can be obtained from suppliers including: International Flavors and Fragrances of New York, NY USA; Givaudan of Vernier Switzerland; Firmenich of Geneva, Switzerland; Symrise of Holzminden, Germany; Kao of Tokyo, Japan; Takasago of Tokyo, Japan; and Florasynth of Tel-Aviv, Israel.
Precursor Silicone Polymers The present disclosure also relates to certain silicone polymers that may, for example, serve as precursors to the pro-fragrance silicone polymers according to the present disclosure. These precursor silicone polymers may be reacted, for example by way of a condensation reaction, with a perfume raw material to form the pro-fragrance silicone polymers of the present disclosure. Thus, these precursors are stand-alone polymers that may act as feedstock polymers or reactants that can be useful to form the pro-fragrance silicone polymers described herein.
Typically, the precursor silicone polymer has one or more portions that include alkanolamine and/or thiol amine moieties, which are capable of reacting with certain aldehyde- or ketone-containing PRMs to form the heterocyclic moieties described herein. The one or more portions with an alkanolamine and/or thiol amine moiety may be connected to a silicone polymer backbone via an organic linker group.
The precursor silicone polymer may comprise at least one radical selected from the group consisting of Formula VI, Formula VII, and mixtures thereof, where the radicals of Formula VI
and Formula VII have the following structures:
(Si) ù X ù Y Formula VI;
(Si) ù X ù (Y ù X)n ù (Si) Formula VII; and where "(Si) ù"is the bond to a silicon atom, for example a silicon atom of a silicone backbone, where the index n is 1 or 2, preferably 1, wherein each X group is an organic linker group, is an independently selected divalent organic group comprising from 2 to 24 chain atoms, and comprises a carbon atom bonded to a silicon atom of a silicone backbone (i.e., each X group is covalently linked to "(Si)" via a Si-C
bond), and wherein each Y group is independently a monovalent or divalent moiety that includes a nitrogen atom and a second atom, where the second atom is selected from the group consisting of an oxygen atom and a sulfur atom, and where the nitrogen atom is separated from the second atom by two atoms, three atoms, or four atoms.
Suitable organic linker / X groups are described in more detail above with regard to the pro-fragrance silicone polymer; the related disclosure above substantially applies equally with respect to the precursor silicone polymer. For example, a carbon atom of the X
moiety is bonded to the silicon atom of the backbone, e.g., via the "(Si) ¨" bond. It is believed that configuration is more stable than if an oxygen of a linker group were to be bonded to the silicon atom. Preferably, the X group is bonded to a non-terminal silicon atom.
In the radicals according to Formula VI and/or Formula VII, the Y group comprises the alkanolamine moiety and/or the thiol amine moiety. The Y groups may be selected so that they are capable of forming a Z group when reacted with an aldehyde- or ketone-containing perfume raw material, as described above.
For example, the Y group may be derivable by the removal from Formula VIII of a moiety selected from RI, one or more monovalent substituents from J, or combinations thereof, where Formula VIII has the following structure:

N (j)rriG.H
Formula VIII, where G is selected from the group consisting of oxygen or sulfur, preferably oxygen;
where the index m is from 2 to 4, preferably m is from 2 to 3, more preferably m is 2;
where R1 is selected from H or a monovalent moiety with a molecular weight between 15 and 495 Da, more preferably R1 is selected from H or a monovalent moiety with a molecular weight between 15 and 101 Da, even more preferably R1 is H; where each J is independently selected from the group consisting of C(R2)2, -0-, and -N(R2)-, where each R2 is independently selected from H and a monovalent moiety with a molecular weight between 14 and 990 Da, more preferably R2 is selected from H and a monovalent moiety with a molecular weight between 14 5 and 186 Da, even more preferably R2 is H, with the proviso that a first unit and a second unit can optionally be taken together, where feasible, as a divalent substituent, where the first unit is a first R2 group, and where the second unit is selected from the group consisting of a second R2 group, the le group, and a monovalent substituent of the R1 group, preferably where the divalent substituent is selected from the group 10 consisting of a fused ring, a spirocyclic ring, an unsaturated substituent, =N(R2), -C(0)-, and -C(S)-; optionally, where a second moiety selected from R', a substituent of IV, one or more monovalent substituents of J, or a combination thereof is replaced with a second link to an X
group, preferably thereby forming a ring structure.
Put somewhat differently, each Y may be independently a monovalent or divalent moiety

15 according to Formula VIII, wherein Formula VIII has the following structure:
R1,, N )rn H
Formula VIII, wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen; wherein the index m is from 2 to 4, preferably m is from 2 to 3, more preferably m is 2; wherein IV is selected from H, a monovalent moiety with a molecular weight between 15 and 500 Da, or a point of attachment of Y to an X group, wherein when Rl is present as the monovalent moiety, 20 the monovalent moiety is preferably a substituted or unsubstituted C i-C35 alkyl group, more preferably a monovalent moiety with a molecular weight of from 15 to 101 Da, even more preferably a substituted or unsubstituted C i-C8 alkyl, preferably wherein R1 is H; wherein each J
is independently selected from the group consisting of C(R2)2, -0-, -N(R2)-, wherein each R2 is independently selected from the group consisting of H, a monovalent moiety with a molecular 25 weight between 14 and 990 Da, or a point of attachment of Y to an X
group, wherein when R2 is present as the monovalent moiety, the monovalent moiety is preferably a substituted or unsubstituted, saturated or unsaturated Ci-C70 alkyl, more preferably a monovalent moiety with a molecular weight of from 14 to 186 Da, even more preferably a substituted or unsubstituted, saturated or unsaturated CI to Cu alkyl, preferably wherein each R2 is H; with the proviso that a first unit and a second unit can optionally be taken together, where feasible, as a divalent substituent, where the first unit is a first R2 group, and where the second unit is selected from the group consisting of a second R2 group, the R1 group, and a monovalent substituent of the le group, preferably where the divalent substituent is selected from the group consisting of a fused ring, a spirocyclic ring, an unsaturated substituent, =N(R2), =0, and =S;
provided that at least one and no more than two of R1, any R2, or combinations thereof is a point of attachment of Y to an X group.
It may be preferred that when G is oxygen and when Y is derivable from the removal of R1, m is not 2 or 3, as it is believed that such compounds are novel and useful for making the premixes and pro-fragrance silicone compounds described herein.
Similar to the discussions of the Z groups above, the term "derivable" in this context does not necessarily mean that the moiety is actually derived from a compound according to Formula VIII. Similarly, the site of (hypothetical) "removal" indicates where the Y
moiety is connected to the X moiety.
It is believed that any of the above-described precursor silicone polymers are suitable for use in forming the presently described pro-fragrance silicone polymers, or in any of the related processes, premixes, or treatment compositions described herein. However, for patentability purposes of the precursor silicone polymer per se, it may be preferred that when G is an oxygen atom, and preferably when the Y group is derivable from the removal of the Rl group (e.g., the Y
group is connected to the X group via the nitrogen group of Formula VIII where the R1 group is shown), m is not 2 or 3.
The precursor silicone polymers of the present disclosure may have a structure according to Formula IX, shown below:
[R5R6R7Si01nkg+2r+2) [R8R9Si02/2]p [R16SiO3/2]q [SiO4/2]r Formula IX
where: q is an integer from 0 to 150; p is an integer from 0 to 1500; r is an integer from 0 to 150;
where q+p+r equals an integer greater than or equal to 1; where each of R5, R6, le, R8, R9 and R1 moiety is independently selected from the group consisting of H, OH, a monovalent organic moiety, a radical according to Formula VI, or a radical according to Formula VII, where at least one of the R5-R1 moieties is a radical according to Formula VI or a radical according to Formula VII, preferably a radical according to Formula VI.
The precursor silicone polymer may be characterized by a weight average molecular weight of from about 450 Da to about 200000 Da, and/or the pro-fragrance silicone polymer may be characterized by a viscosity comprised in the range between 0.004 (Pa*s) and 100 (Pa*s).
Methods for determining the weight average molecular weight and the viscosity of silicone polymers are provided in the Test Method section below. Such molecular weights and/or viscosities may be preferred because it is believed that they lead to improved surface deposition, formulation stability, and affinity with perfume raw materials.
The precursor silicone polymer comprises nitrogen atoms. The precursor silicone polymer may be characterized by a total amine content of from about 0.05 to about 2.2, preferably from about 0.071 to about 2.14, or from about 0.071 to about 1.78, or from about 0.71 to about 1.43, or from about 0.14 to about 1.07, or from about 0.14 to about 0.71, or from about 0.21 to about 0.71, or from about 0.36 to about 0.71. The precursor silicone polymer may be characterized by a nitrogen content of from about 0.1% to about 3%, or from about 0.1% to about 2%, or from about 0.2% to about 1.5%, or from about 0.2% to about 1.0%, or from about 0.3% to about 0.8%, or from about 0.3% to about 0.75%, reported as functional group equivalent weight %. The amine content and functional group equivalent weight percentage can be determined according to the methods provided in the Test Methods section. Nitrogen levels that are too low may lead to poor PRM loading; nitrogen levels that are too high may lead to increases in water solubility and/or poorer performance.
A precursor silicone polymer may be obtained from the combination of an appropriately functionalized homopolymer, copolymer, or higher oligomer silicone and an appropriate matching small molecule additive (e.g. amine, oxirane, alkanolamine, thiirane etc.), with or without a cosolvent catalyst (alcohol, diol, acids, bases), with or without external stimuli (e.g.
pressure, heat, mechanical stirring), with or without catalyst, and with or without purification.
In the present disclosure a silicone polymer precursor may be obtained from polymerization of individual silane compounds to reach a silicone polymer as described in Formula IX of the appropriate composition and functionality.

Method of Making a Pro-Fragrance Silicone Polymer and Related Premixes The present disclosure also relates to methods of making pro-fragrance silicone polymers according to the present disclosures, as well as related premixes.
The present disclosure relates to a method of making a pro-fragrance silicone polymer. The method may comprise the step of combining a precursor silicone polymer as described above with a suitable perfume raw material, namely one that comprises an aldehyde moiety, a ketone moiety, or a combination thereof.
The combining step may occur at any suitable point, for example in a premix, in a base composition, or even on a surface or article, such as a fabric article, which may be accompanied by the removal of water (e.g., via a drying process).
The precursor silicone polymer and the one or more perfume raw materials may be combined in a treatment composition, for example by adding each as separate inputs to a base composition.
The precursor silicone polymer and the perfume raw material may be combined in a liquid premix composition. Thus, the present disclosure relates to such liquid premix compositions and methods of making such liquid premix compositions.
The liquid premix compositions of the present disclosure (also referred to herein as "premix compositions" or even just "premixes" or "a premix") may be useful components of treatment compositions and may help to improve perfume delivery and performance of those compositions compared to products where such a premix is not used. Further, it is believed that combining the ingredients in a premix provide more efficient perfume delivery and performance in a treatment compared to if the ingredients are added separately (e.g., not as a premix) to the consumer product, particularly in aqueous consumer products. Additionally, premix compositions may be conveniently made in advance and stored and/or transported between locations as desired, or even made by a third party prior to incorporation into a treatment composition.
The present disclosure relates to a method of making a premix composition, preferably a premix composition as described herein. The method comprises the steps of:
providing a precursor silicone polymer, which may comprise one or more radicals according to Formula VI, Formula VII, or mixtures thereof, as described in more detail above; and combining the precursor silicone polymer with a perfume raw material that comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and a combination thereof. As described in more detail below, the precursor silicone polymer may be combined with an emulsifier, preferably a nonionic surfactant, to form an oil-in-water emulsion, to which the PRM may be added.
The liquid premix composition may comprise: (a) a pro-fragrance silicone polymer as described herein, for example a pro-fragrance silicone polymer comprising at least one radical selected from the group consisting of Formula I, Formula II, and mixtures thereof, as described in more detail above, and optionally further comprising one or more free perfume raw materials; or (b) a precursor silicone polymer, which may comprise one or more radicals according to Formula VI, Formula VII, or combinations thereof; as described in more detail above, and a perfume raw material that comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and a combination thereof, wherein the precursor silicone polymer and the perfume raw material are capable of condensing to form the pro-fragrance silicone polymer; or (c) a mixture thereof.
The liquid premix composition may comprise, by weight of the liquid premix composition, the precursor silicone polymer present at a level of from about 1% to about 99%, preferably from about 80% to about 10%, or from about 75% to about 20%, or from about 60% to 40%, and the perfume raw material present at a level of from about 1% to 50%, preferably from about 5% to about 50%, or from about 5% to about 30%, or from about 5% to about 20%, or from about 5% to about 15%, or from about 5% to about 10%. The PRMs may be present, by weight of the liquid premix composition, of from about 10% to about 40%, or from about 15% to about 30%, or from about 15% to about 25%. An optional amount of emulsifier may be present at a level from about 0% to about 10%, preferably from about 1% to about 5%, or from about 2% to 4%.
The weight ratio of the precursor silicone polymer and the perfume raw material may be from about 99:1 to about 1:1, preferably from about 50:1 to about 2:1, more preferably from about 10:1 to about 5:1.
Preferred amounts and/or ratios are desirable to achieve convenient and efficient payload delivery.
The premix compositions typically are liquids. The liquid premix composition may be characterized by a viscosity, for example from about 10 to about 10000 Pa- s, preferably from about 10 to about 5000 Pas, preferably from about 10 to about 1000 Pas, preferably from about 10 to about 500 Pa.s, preferably from about 20 to about 400 Pa- s, more preferably from about 25 to about 300 Pa. s, even more preferably from about 100 to about 300 Pa.s, measured at 0.1 rad/s and 25 C. Obtaining a liquid premix composition with the target viscosity may be desirable for processability reasons, particularly as premixes having a very high viscosity may be difficult to formulate into a product.
The liquid premix composition may be substantially free of water. The premix composition may comprise less than 10%, or less than 5%, or less than 2%, or less than 1%, or less than 0.5%, 5 or less than 0.1%, or even comprise 0%, by weight of the premix composition of water. Such low-water premixes may be desirable, for examples, when the premix will be formulated into a low-water consumer product, such as a solid composition (particularly when water-soluble) or a composition encapsulated by water-soluble film. In such cases, the silicone polymer may be a fluid that is the bulk of the premix.
10 The fragrance premix composition may comprise water. The fragrance premix composition may comprise from about 1% to about 90%, or from about 1% to about 75%, or from about 1% to about 60%, or from about 1% to about 50%, or from about 5% to about 50%, or from about 5% to about 25%, or from about 5% to about 15%, or from about 5% to about 10%, by weight of the composition, of water. The fragrance premix composition may comprise from about 10% to about 15 50%, or from about 25% to about 50%, by weight of the composition of water. The presence of water may facilitate the formation of droplets, in view of the silicone polymer being relatively hydrophobic, which can facilitate more convenient dispersion of the premix in a treatment composition, particularly those that are aqueous.
The liquid premix composition may be in the form of an emulsion. The emulsion may preferably be an oil-in-water emulsion. The emulsion may comprise a plurality of droplets, preferably comprising droplets characterized by a volume-weighted average particle size of from about 100 nm to about 100 gm, more preferably from 1 gm to 10 gm, even more preferably from 1 gm to 5 gm. Without wishing to be bound by theory, it is believed that droplets of a certain minimum size are desired for efficiency of deposition onto the target surface, but that droplets that exceed a certain size can create performance and/or stability issues, such spotting on the target surface.
The liquid premix composition may comprise one or more emulsifiers. As used herein, "emulsifier(s)" and "emulsifying agent(s)" are used interchangeably. Selection of proper emulsifier can facilitate the formation of droplets of the desired size, and/or the stable incorporation 30 of the premix into a final product. Emulsifiers may also be selected so as to not have an undesirable impact on viscosity of the emulsion, for example by increasing the viscosity to an undesirable level.

The emulsifier may be present at a level of from about 0.5% to about 40%, preferably from about 1% to about 30%, more preferably from about 1% to about 20%, more preferably from about 2% to about 20%, more preferably from about 2% to about 10%, by weight of the liquid premix composition. The emulsifier may be present in an amount of from about 1% to about 10%, more preferably from 1% to about 5% by weight of the liquid premix composition. The weight ratio of the precursor silicone polymer to the emulsifier may be from about 99:1 to about 1:1, preferably from about 50:1 to about 2:1, more preferably from about 15:1 to about 5:1.
The liquid premix composition may comprise from about 20% to about 40% water, and from about 1%
to about 5%
emulsifier, by weight of the liquid premix composition.
The one or more emulsifiers may comprise a nonionic surfactant. Suitable nonionic surfactant may include alkoxylated fatty alcohols. The nonionic surfactant may be selected from ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(0C21-14)11OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
The one or more emulsifiers may comprise linear emulsifiers, branched emulsifiers, or mixtures thereof; preferably linear nonionic surfactants, branched nonionic surfactants, or mixtures thereof. In particular, linear emulsifiers may be useful for emulsifying the perfume raw materials, and branched emulsifiers may be useful for emulsifying the silicone polymer, particularly amino-modified silicone polymers.
The one or more emulsifiers may be substantially hydrophobic. The one or more emulsifiers may be characterized by an HLB value of from about 5 to about 20, or from about 8 to about 16. The HLB value of a nonionic surfactant may be determined according to the method provided below.
The liquid premix compositions of the present disclosure may further comprise an aminofunctional material as an additional ingredient. It is believed that the aminofimetional material can associate with the perfume raw materials and perhaps even the silicone materials described herein and facilitate the deposition and release of the perfume when used as part of a treatment composition.

The liquid premix composition may comprise from about 1% to about 20%, or from about 2% to about 15%, or from about 3% to about 12%, or from about 4% to about 10%, or from about 5% to about 10%, by weight of the fragrance premix composition, of the aminofunctional material.
The aminofunctional material may be characterized by a relatively low molecular weight.
Relatively low molecular weights may be preferred for mass efficiency reasons (e.g. a favorable /
high ratio of amine groups to molecular weight). For example, the aminofunctional material may be characterized by a molecular weight of about 17 to about 1000 Daltons, more preferably from about 30 to about 1000 Daltons, 40 to about 1000 Daltons, preferably from about 50 to 800 Daltons, more preferably from about 60 to about 600 Daltons, even more preferably from about 60 to about 500 Daltons.
The aminofunctional material may comprise one, two, or three amine moieties per molecule, preferably one or two amine moieties. The amine moiety may be selected from the group consisting of a primary amine moiety, a secondary amine moiety, or a combination thereof. It is believed that primary and/or secondary amine moieties may better associate with the PRMs compared to tertiary and/or quaternary amine moieties. Furthermore, two or even three amine moieties may provide improved association / loading in combination with the perfume raw materials, compared to compounds having only one amine group. However, as described in more detail below, there may be a desire to limit the number of amine groups.
It is believed that certain aminofunctional materials are likely to work better than others in the compositions of the present disclosure due to their amine moiety type and/or structure. For example, the aminofunctional material may be characterized by one of the following: (a) comprising a total of one primary amine moiety and no secondary amine moieties; or (b) comprising a total of two primary amine moieties and no secondary amine moieties; or (e) one primary amine moiety and one secondary amine moiety, preferably where the primary amine moiety and the secondary amine moiety are separated by two carbon atoms; or (d) one primary amine moiety or secondary amine moiety that is separated by two carbon atoms from a hydroxyl group.
The aminofunctional material may be selected from: linear aliphatic aminofunctional materials, such as octylamine, nonylamine, and/or decylamine; branched aliphatic aminofunctional materials, such as 2-ethylhexylamine, branched tridecylamine, t-butylamine, 2-(diethylamino) ethylamine, neopentanediamine (2,2-dimethyl propane-1,3-diamine), 3-methoxyethylamine, trimethy1-1,6-hexanediamine, 2-am inoheptane, and/or 2-butyloctylamine;
cycloaliphatic amines, including methylcyclohexane diamines such as 2-methylcyclohexane-1,3-diamine and/or 4-methylcyclohexane-1,3 -diam ine ; aminofunctional silanes, such as trialkoxy(aminoethylaminopropyl)silane, alkyl dialkoxy(aminoethylaminopropyl)silane, dialkyl alkoxy(aminoethylaminopropyl)silane, trialkoxy(aminopropyl)silane, alkyl dialkoxy(aminopropyl)silane, and/or dialkyl alkoxy(aminopropyl)silane;
aminoalcohols, such as 2-(butylamino)ethanol, 1-(cyclohexylamino)2-propanol, 1-(dodecyloxy)-3-[(2-hydroxyethyDamino]-2-propanol, and/or 3-(dodecylamino)-1,2-propanediol; 1,3 -bis(3 -aminopropyl) tetramethyldisiloxane; or mixtures thereof.
The aminofunctional material may be substantially free of aromatic amines (e.g., where an aminofunctional moiety is directly attached to an aromatic ring), or even substantially free of aromatic moieties altogether, as such moieties tend to increase the solubility of the aminofunctional material and therefore may make it less likely to associate with the hydrophobic silicone.
The liquid premix composition may be made according to any suitable process.
For example, the present disclosure relates to a process of making a premix composition, such as those described herein, where the process includes the steps (preferably in order) of: providing the silicone polymer precursor; adding the aminofunctional material, if any; and adding the perfume raw materials; where each is provided in the relative amounts described above.
Mixing may be provided throughout or intermittently. The resulting mixture may be mixed with sufficient mixing energy to combine the materials.
When it is desired that the fragrance premix composition is in the form of an emulsion, the process may include the steps (preferably in order) of: providing the silicone polymer precursor;
adding the aminofunctional material, if any; adding an emulsifying agent;
adding the water; and adding the perfume raw material; where each is provided in the relative amounts described above.
Mixing may be provided throughout or intermittently. The resulting mixture may be mixed with sufficient mixing energy to combine and emulsify the materials, for example to form the droplets described above.
The process may include the steps (preferably in order) of: providing the silicone polymer precursor; adding an emulsifying agent; adding the water; adding the aminofunctional material, if any; and adding the perfume raw materials; where each is provided in the relative amounts described above. Mixing may be provided throughout or intermittently. The resulting mixture may be mixed with sufficient mixing energy to combine and emulsify the materials, for example to form the droplets described above.
Certain components may be premixed, for example, the silicone polymer precursor and an emulsifying agent, and/or the fragrance material and an emulsifying agent. The emulsifying agents for each material may be the same, or they may be different.
Treatment Compositions The present disclosure also relates to treatment compositions that include pro-fragrance silicone polymers as described above, as well as methods of making and using such treatment compositions. The treatment compositions may further include a treatment adjunct.
The treatment compositions may be consumer product compositions. The consumer product compositions may be useful for treating a surface, for example to freshen and/or condition the surface, such as fabric, hair, or skin. Suitable consumer product compositions are described above. Preferred consumer product compositions may include baby care compositions, personal care compositions, fabric care compositions, home care compositions, family care compositions, and/or feminine care compositions, preferably fabric care compositions and/or home care compositions, more preferably fabric care compositions.
The treatment compositions may comprise a liquid premix composition, for example in emulsion form, according to the present disclosure and a treatment adjunct.
The treatment compositions may be made by providing a premix composition according to the present disclosure, and combining the premix with a treatment adjunct. The treatment adjunct may be part of a base composition.
The treatment compositions may comprise a pro-fragrance silicone polymer according to the present disclosure at a level of from about 0.01% to about 99.9%, by weight of the treatment composition, preferably from about 0.01% to about 50%, more preferably from about 0.01% to about 25%, more preferably from about 0.1% to about 10%, more preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 5%, by weight of the treatment composition.
The levels may be dictated by the intended fmal use and form of the treatment composition.
The treatment compositions described herein may comprise from about 0.1% to about 20%, or from about 0.1% to about 15%, or from about 0.1% to about 10%, or from about 0.1% to about 5%, or from about 0.1% to about 3%, by weight of the treatment composition, of a liquid premix composition according to the present disclosure.
The treatment composition may comprise one or more of the following components at one or more of the following levels, where the component(s) is provided by a liquid premix, and where 5 the weight percentages are by weight of the treatment composition: from about 0.1% to about 20%
of the silicone polymer, and/or from about 0% to about 10% of the aminofunctional material (if any), and/or from about 0.05% to about 20% of one or more perfume raw materials.
The present disclosure also relates to a treatment composition that comprises a treatment adjunct and a plurality of droplets, wherein the droplets comprise: a silicone polymer precursor as 10 described above; optionally an aminofunctional material as described above; optionally emulsifiers as described above; and a perfume raw material as described above; where the components are present in the droplet in the relative amounts as described above.
Additionally or alternatively, the droplets may comprise a pro-fragrance silicone polymer according to the present disclosure. The droplets may be present in the treatment composition as a result of combining a liquid premix 15 composition as described herein with a treatment adjunct. The plurality of droplets may be characterized as having a volume-weighted average diameter of from about 1 micron to about 10 microns, preferably from about 1 micron to about 5 microns.
The treatment compositions according to the present disclosure may be in the form of a liquid composition, a granular composition, a single-compartment pouch, a multi-compartment 20 pouch, a dissolvable sheet, particulate form where individual particles have a mass of from about lmg to about 1 gram (such as a pastille or bead, which may preferably be water-soluble), a fibrous article, a tablet, a bar, a flake, a non-woven sheet, or a mixture thereof.
The treatment compositions of the present disclosure may be a household care composition, preferably a household care composition selected from the group consisting of a fabric and home 25 care product, a beauty care product, or a mixture thereof When the treatment composition is a fabric and home care product, the fabric and home care product may preferably be selected from a laundry detergent composition, a fabric conditioning composition, a fabric pre-treatment composition, a fabric refresher composition, or a mixture thereof. The fabric conditioning composition may preferably be a liquid fabric 30 conditioning composition.

When the treatment composition is a beauty care product, the beauty care product may preferably be selected from a hair treatment product, a skin care product, a shave care product, a personal cleansing product, a deodorant and/or antiperspirant, or a mixture thereof. The hair treatment composition preferably may preferably be a shampoo, a conditioner, or a combination thereof.
The treatment composition may include a treatment adjunct, in addition to the fragrance premix composition and/or droplets. The treatment adjunct may be any adjunct ingredient, in any amount, that is suitable for the intended product and/or intended end-use of the product. The treatment composition may be made by a method that comprises the step of combining the fragrance premix composition with the treatment adjunct.
The treatment adjunct may be part of a base composition that is combined with the liquid premix composition. For example, the present disclosure relates to a method of making a treatment composition that includes the step of combining a premix composition with a base composition, where the base composition comprises a treatment adjunct. The premix composition may be added to the base composition. Treatment adjuncts may be added to the base composition before and/or after the premix composition is added to the base composition. It is understood that as used herein, a "base composition" is an intermediate composition, to which other ingredients may be added to form a completed or final treatment composition.
Treatment adjuncts may be useful as performance aids, stability or processing aids, or both.
For example, the treatment adjunct may be selected from an amine, a surfactant system, a water-binding agent, a sulfite, fatty acids and/or salts thereof, enzymes, encapsulated benefit agents, soil release polymers, hueing agents, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzyme stabilizers, catalytic materials, bleaching agents, bleach catalysts, bleach activators, polymeric dispersing agents, soil removal/anti-redeposition agents, polymeric dispersing agents, polymeric grease cleaning agents, brighteners, suds suppressors, dyes, hueing agents, free perfume, structure elasticizing agents, conditioning or softening agents, carriers, fillers, hydrotropes, organic solvents, anti-microbial agents and/or preservatives, neutralizers and/or pH
adjusting agents, processing aids, fillers, rheology modifiers or structurants, pacifiers, pearlescent agents, pigments, anti-corrosion and/or anti-tarnishing agents, malodor agents, and mixtures thereof. While one of ordinary skill will generally be familiar with these adjuncts, a few of the adjuncts are described in more detail below.

The treatment compositions may include surfactant. Surfactants may be useful for providing, for example, cleaning benefits. The compositions may comprise a surfactant system, which may contain one or more surfactants.
The compositions of the present disclosure may include from about 1% to about 70%, or from about 2% to about 60%, or from about 5% to about 50%, by weight of the composition, of a surfactant system. Liquid compositions may include from about 5% to about 40%, by weight of the composition, of a surfactant system. Compact formulations, including compact liquids, gels, and/or compositions suitable for a unit dose form, may include from about 25%
to about 70%, or from about 30% to about 50%, by weight of the composition, of a surfactant system.
The surfactant system may include anionic surfactant, nonionic surfactant, zwitterionic surfactant, cationic surfactant, amphoteric surfactant, or combinations thereof. The surfactant system may include linear alkyl benzene sulfonate, alkyl ethoxylated sulfate, alkyl sulfate, nonionic surfactant such as ethoxylated alcohol, amine oxide, or mixtures thereof The surfactants may be, at least in part, derived from natural sources, such as natural feedstock alcohols.
Suitable anionic surfactants may include any conventional anionic surfactant.
This may include a sulfate detersive surfactant, for e.g., alkoxylated and/or non-alkoxylated alkyl sulfate materials, and/or sulfonic detersive surfactants, e.g., alkyl benzene sulfonates. The anionic surfactants may be linear, branched, or combinations thereof. Preferred surfactants include linear alkyl benzene sulfonate (LAS), alkyl ethoxylated sulfate (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched modified alkyl benzene sulfonates (MLAS), methyl ester sulfonates (MES), sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), and/or alkyl ethoxylated carboxylates (AEC). The anionic surfactants may be present in acid form, salt form, or mixtures thereof. The anionic surfactants may be neutralized, in part or in whole, for example, by an alkali metal (e.g., sodium) or an amine (e.g., monoethanolamine).
The surfactant system may include nonionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohols, such as ethoxylated fatty alcohols. Other suitable nonionic surfactants include alkoxylated alkyl phenols, alkyl phenol condensates, mid-chain branched alcohols, mid-chain branched alkyl alkoxylates, alkylpolysaccharides (e.g., alkylpolyglycosides), polyhydroxy fatty acid amides, ether capped poly(oxyalkylated) alcohol surfactants, and mixtures thereof. The alkoxylate units may be ethyleneoxy units, propyleneoxy units, or mixtures thereof.
The nonionic surfactants may be linear, branched (e.g., mid-chain branched), or a combination thereof. Specific nonionic surfactants may include alcohols having an average of from about 12 to about 16 carbons, and an average of from about 3 to about 9 ethoxy groups, such as Cl 2-C14 E07 nonionic surfactant.
Suitable zwitterionic surfactants may include any conventional zwitterionic surfactant, such as betaines, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, C8 to Cu (for example from C12 to C18) amine oxides (e.g., C12-14 dimethyl amine oxide), and/or sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-l-propane sulfonate where the alkyl group can be C8 to C18, or from Cu) to C14. The zwitterionic surfactant may include amine oxide.
Depending on the formulation and/or the intended end-use, the composition may be substantially free of certain surfactants. For example, liquid fabric enhancer compositions, such as fabric softeners, may be substantially free of anionic surfactant, as such surfactants may negatively interact with cationic ingredients.
The treatment compositions may include conditioning actives. Compositions that contain conditioning actives may provide softness, anti-wrinkle, anti-static, conditioning, anti-stretch, color, and/or appearance benefits.
Conditioning actives may be present at a level of from about 1% to about 99%, or from about 1% to about 35%, or from about 1% to about 20%, or from about 1% to about 15%, or from about 1% to about 10%, or from about 1% to about 6%, by weight of the composition. The composition may include from about 1%, or from about 2%, or from about 3%, to about 99%, or to about 75%, or to about 50%, or to about 40%, or to about 35%, or to about 30%, or to about 25%, or to about 20%, or to about 15%, or to about 10%, by weight of the composition, of conditioning active. The composition may include from about 5% to about 30%, by weight of the composition, of conditioning active.
Conditioning actives suitable for compositions of the present disclosure may include quaternary ammonium ester compounds, silicones, non-ester quaternary ammonium compounds, amines, fatty esters, sucrose esters, dispersible polyolefins, polysaccharides, fatty acids, softening or conditioning oils, polymer latexes, or combinations thereof, preferably at last quaternary ammonium ester compounds, as such materials are known to provide useful conditioning benefits while also being relatively environmentally friendly.

The composition may include a quaternary ammonium ester compound, a silicone, or combinations thereof, preferably a combination. The combined total amount of quatemary ammonium ester compound and silicone may be from about 5% to about 70%, or from about 6%
to about 50%, or from about 7% to about 40%, or from about 10% to about 30%, or from about 15% to about 25%, by weight of the composition. The composition may include a quaternary ammonium ester compound and silicone in a weight ratio of from about 1:10 to about 10:1, or from about 1:5 to about 5:1, or from about 1:3 to about 1:3, or from about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1, or about 1:1.
The composition may contain mixtures of different types of conditioning actives. The compositions of the present disclosure may contain a certain conditioning active but be substantially free of others. For example, the composition may be free of quaternary ammonium ester compounds, silicones, or both. The composition may comprise quaternary ammonium ester compounds but be substantially free of silicone. The composition may comprise silicone but be substantially free of quaternary ammonium ester compounds.
The compositions of the present disclosure may contain a rheology modifier and/or a structurant. Rheology modifiers may be used to "thicken" or "thin" liquid compositions to a desired viscosity. Structurants may be used to facilitate phase stability and/or to suspend or inhibit aggregation of particles or droplets in liquid compositions, such as the droplets of the emulsions as described herein. Suitable rheology modifiers and/or structurants may include non-polymeric crystalline hydroxyl functional structurants (including those based on hydrogenated castor oil), polymeric structuring agents, cellulosic fibers (for example, mierofibrillated cellulose, which may be derived from a bacterial, fungal, or plant origin, including from wood), di-amido gellants, or combinations thereof.
The treatment compositions made from the presently described methods may include free perfume. To provide a broader and more diverse scent profile, it may be desirable to include perfume raw materials in the free perfume of the treatment composition that are not present in the pro-fragrance silicone, and/or vice versa. For example, when the pro-fragrance silicone polymer comprises a fragment or residue of one or more perfume raw materials that comprise an aldehyde moiety, the free perfume of the treatment composition may comprise one or more perfume raw materials that do not comprise an aldehyde moiety. Similarly, when the pro-fragrance silicone polymer comprises a fragment or residue of one or more perfume raw materials that comprise a ketone moiety, the free perfume of the treatment composition may comprise one or more perfume raw materials that do not comprise a ketone moiety. The free perfume may include perfume raw materials that include aldehyde moieties, perfume raw materials that do not include aldehyde moieties, perfume raw materials that include ketone moieties, perfume raw materials that do not include ketone moieties, or mixtures thereof.
5 The treatment composition may comprise a carrier material. The carrier material may be selected from the group consisting of water, silica, zeolite, carbonate, polyvinyl alcohol, polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxoalkylene, polyethylene glycol fatty acid ester, polyethylene glycol ether, sodium sulfate, starch, and mixtures thereof. The carrier material may be selected based on 10 the desired final form of the consumer product; for example, a liquid product may use water as a carrier, whereas a powdered or particle product may use carbonate or polyethylene glycol (PEG).
The base composition may be in the form of a liquid. The base composition may comprise water. The base composition may comprise from about 1% to about 99%, preferably from about 5% to about 98%, or from about 10% to about 95%, or from about 50% to about 95%, or from about 60% to about 95%, or from about 75% to about 95%, by weight of the base composition, of water.
The treatment composition may be in the form of a liquid. The treatment composition may comprise water. The treatment composition may comprise from about 1% to about 99%, preferably from about 5% to about 98%, or from about 10% to about 95%, or from about 50%
to about 95%, 20 or from about 60% to about 95%, or from about 75% to about 95%, by weight of the treatment composition, of water. Certain unit dose formulations may have relatively low amounts of water so as to not dissolve the water-soluble film; for example, the composition may comprise no more than about 20%, or no more than about 15%, or no more than about 12%, or no more than about 10%, by weight of the composition, of water. The fragrance premixes of the present disclosure 25 may be particularly useful in liquid compositions that include a relatively high amount of water, as it is believed the hydrophobicity of the silicone enables the silicone, aminofunctional material, emulsifiers, and fragrance material to partition from the water and to associate in the high-water matrix.
The liquid treatment composition may have a viscosity from about 20 cps to about 1000 30 cps (about 20-1000 mPa- s), preferably from about 25 cps to about 500 cps (about 25-500 mPa-s), more preferably from about 50 cps to about 300 cps (about 50 mPa.s to about 300 mPa.$). The viscosity is determined using a Brookfield viscometer, No. 2 spindle, at 60 RPM/s, measured at about 22 C.
The treatment composition may be in a particulate form, such as a plurality of particulates.
Individual particulates may have a mass from about 1 mg to about 1 g. The emulsion may be dispersed in a water-soluble carrier. The water-soluble carrier may be selected from the group consisting of polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxoalkylene, polyethylene glycol fatty acid ester, polyethylene glycol ether, sodium sulfate, starch, and mixtures thereof. The water-soluble carrier may be a water-soluble polymer. The treatment composition, when in particulate form, may comprise from about 25wt% to about 99.99wt% of the water-soluble carrier, and from about 0.01wt% to about 50wt% by weight the silicone premix. The particulate form may be in the form of a bead or pastille.
The treatment composition may be characterized by a pH level of from about 2 to about 12, or from about 2 to about 8.5, or from about 2 to about 7, or from about 2 to about 5, preferably from about 2 to about 4, preferably a pH of from about 2 to about 3.7, more preferably a pH from about 2 to about 3.5, wherein pH is determined by dissolving/dispersing the treatment composition in deionized water to form a solution at 10% concentration, at about 20 C.
Methods of Making Treatment Compositions The present disclosure relates to processes for making any of the treatment compositions described herein.
The method may comprise the steps of: providing a base composition, wherein the base composition comprises a treatment adjunct; and combining the base composition with one or more of the following: (a) a pro-fragrance silicone polymer as described herein, for example one comprising one or more radicals according to Formula I, Formula II, or mixtures thereof; (b) a precursor silicone polymer as described herein, for example one comprising one or more radicals according to Formula VI, Formula VII, or combinations thereof, and a perfume raw material that comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and a combination thereof, preferably wherein the precursor silicone polymer and the perfume raw material are provided as a liquid premix composition, preferably in emulsion form; and/or (c) a mixture thereof. The compositions described above may optionally be combined with an aminofunctional compound.

4.' The precursor silicone polymer and the perfume raw material may preferably be provided as a premix composition, preferably a liquid premix composition, more preferably a liquid premix in emulsion form, to the base composition. The precursor silicone polymer and the perfume raw material may preferably be provided as separate inputs to the base composition. The separate inputs may occur concurrently or sequentially. When occurring sequentially, it is preferred that the precursor silicone polymer, which may preferably be emulsified, is added prior to the addition of the perfume raw material. The mixture may be mixed to homogenize the resulting composition.
The treatment compositions of the present disclosure can be formulated into any suitable form and prepared by any process chosen by the formulator. The materials may be combined in a batch process, in a circulation loop process, and/or by an in-line mixing process. Suitable equipment for use in the processes disclosed herein may include continuous stirred tank reactors, homogenizers, turbine agitators, recirculating pumps, paddle mixers, high shear mixers, static mixers, plough shear mixers, ribbon blenders, vertical axis granulators and drum mixers, both in batch and, where available, in continuous process configurations, spray dryers, and extruders.
Methods of Using Treatment Compositions The present disclosure also relates to a method of treating a surface, where the method comprises the step of contacting the surface with a treatment composition described herein, optionally in the presence of water. Preferably, the surface is a fabric, hair, or skin, more preferably a fabric, even more preferably a garment.
The processes of the present disclosure may include diluting the composition with water to form a treatment liquor, which may contact the surface to be treated. The composition may be diluted from 100-fold to 1000-fold, or from 200-fold to 900-fold, or from 300-fold to 800-fold, by water.
The contacting step may occur in the drum of an automatic washing machine. The contacting step may occur as part of, or shortly before, a wash cycle; for example, the consumer product may be a detergent composition or may be added substantially concurrently with a detergent composition. The contacting step may occur as part of a rinse cycle, which may follow a wash cycle; for example, the consumer product may be a fabric enhancer product, such as a liquid fabric enhancer product, and may contact the surface subsequent to the surface having been treated by a detergent product.

The contacting step may occur as a pretreatment step, for example prior to a wash cycle.
Uses The present disclosure relates to the use of a pro-fragrance silicone polymer according to the present disclosure as a perfuming agent. The pro-fragrance silicone polymer may be used as a perfuming agent on a surface, preferably on a fabric. For such uses, the pro-fragrance silicone polymer may optionally be formulated in a treatment composition, as described in more detail above.
Article and/or Surface The present disclosure relates to an article, preferably a fabric article, comprising a surface, where the surface comprises a pro-fragrance silicone polymer according to the present disclosure.
The present disclosure also relates to an article, preferably a fabric article or a dryer sheet or an absorbant article (such as a diaper or incontinence product), that has been treated with a treatment composition according to the present disclosure, preferably according to a treatment method as described herein.
The present disclosure also relates to a surface, such as a hard surface, comprising a pro-fragrance silicone polymer according to the present disclosure. The present disclosure also relates to a surface, preferably a hard surface, that has been treated with a treatment composition according to the present disclosure, preferably according to a treatment method as described herein.
COMBINATIONS
Specifically contemplated combinations of the disclosure are herein described in the following lettered paragraphs. These combinations are intended to be illustrative in nature and are not intended to be limiting.
A. A treatment composition comprising a treatment adjunct and a pro-fragrance silicone polymer, wherein the pro-fragrance silicone polymer comprises a silicone backbone, an organic linker group comprising a carbon atom bonded to a silicon atom of the silicone backbone, and a heterocyclic moiety bonded to the organic linker group, the heterocyclic moiety comprising from five to seven ring members, the ring members comprising: a first ring member that is a nitrogen atom; a second ring member that is a carbon atom; wherein the second ring member is part of a residue of a perfume raw material ("PRM"), wherein the PRM that formed the residue comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and a combination thereof; a third ring member selected from the group consisting of an oxygen atom or a sulfur atom, preferably an oxygen atom, wherein the second ring member is directly bonded to the first ring member and the third ring member.
B. The treatment composition according to paragraph A, wherein the pro-fragrance silicone polymer comprises at least one radical selected from the group consisting of Formula I, Formula II, and mixtures thereof; wherein the radicals of Formula I and Formula II have the following structures:
(Si) ¨ X ¨ Z Formula I
(Si) ¨ X ¨ (Z ¨ X). ¨ (Si) Formula II
wherein "(Si) ¨" represents the bond to an Si atom, wherein each X group is the organic linker group and is an independently selected divalent organic moiety group comprising from two to twenty-four chain atoms, wherein the Z group comprises the heterocyclic moiety, and wherein the index n is 1 or 2, preferably 1.
C. The treatment composition according to any of paragraphs A or B, wherein the at least one radical has the structure of Formula I.
D. The treatment composition according to any of paragraphs A-C, wherein the PRM
that formed the residue comprises an aldehyde moiety, preferably wherein the PRM is selected from the group consisting of: methyl nonyl acetaldehyde: benzaldehyde;
floralozone;
isocyclocitral; triplal (ligustral); precylcemone B; lilial; decyl aldehyde;
undecylenic aldehyde;
cyclamen homoaldehyde; cyclamen aldehyde; dupical; oncidal; adoxal; melonal;
calypsone;
anisic aldehyde; heliotropin; cuminic aldehyde; scentenal; 3,6-dimethylcyclohex-3-ene-1-carbaldehyde; satinaldehyde; canthoxal; vanillin; ethyl vanillin; cinnamic aldehyde; and mixtures thereof.
E. The treatment composition polymer according to any of paragraphs A-D, wherein the PRM that formed the residue comprises a ketone moiety, preferably wherein the PRM is selected from the group consisting of: nerolione; 4-(4-methoxyphenyl)butan-2-one; 1-naphthalen-2-ylethanone; nectaryl; trimofix 0; fleuramone; delta-damascone; beta-damascone;
alpha-damascone; methyl ionone; 2-hexylcyclopent-2-en-1-one; galbascone; and mixtures thereof.

F. The treatment composition according to any of paragraphs A-E, wherein each X group is independently a divalent organic group having a molecular weight between about 14 and about 1000 Da, preferably between about 28 and about 495 Da, more preferably between about 42 and about 98 Da.
5 G. The treatment composition according to any of paragraphs A-F, wherein each X group independently comprises from two to twelve chain atoms, preferably from two to twelve chain atoms, more preferably from two to nine chain atoms, more preferably from two to six chain atoms, even more preferably wherein at least one of the chain atoms is an oxygen atom, even more preferably wherein the X group is a four-carbon ether group, most preferably wherein the X
10 group is -CH2-CH2-CH2-0-CH2-.
H. The treatment composition according to any of paragraphs A-G, wherein the X
group is bonded to a non-terminal silicon atom.
I. The treatment composition according to any of paragraphs A-H, wherein each Z is a monovalent or divalent heterocyclic moiety derivable by the removal from Formula III of a 15 moiety selected from the group consisting of R', one or more monovalent sub stituents of J, or combinations thereof, wherein formula III has the following structure:
(J )1-1 R1 ________________________________________ N
\
R3 R4 Formula III, wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen; wherein the index m is from 2 to 4, preferably m is from 2 to 3, more preferably m is 2; wherein R1 is 20 selected from H or a monovalent moiety with a molecular weight between 15 and 495 Da, more preferably R1 is selected from H or a monovalent moiety with a molecular weight between 15 and 101 Da, even more preferably R1 is H; wherein each J is independently selected from the group consisting of C(R2)2, -0-, -N(R2)-, wherein each R2 is independently selected from H, a monovalent moiety with a molecular weight between 14 and 990 Da, more preferably R2 is 25 selected from H, a monovalent moiety with a molecular weight between 14 and 186 Da, even more preferably R2 is H; with the proviso that a first unit and a second unit can optionally be taken together, where feasible, as a divalent substituent, where the first unit is a first R2 group, and where the second unit is selected from the group consisting of a second R2 group, the R1 group, and a monovalent substituent of the R1 group, preferably where the divalent substituent is selected from the group consisting of a fused ring, a spirocyclic ring, an unsaturated substituent, =N(R), -C(0)-, and -C(S)-; wherein the -C(10(124)- moiety is the residue of a perfume raw material (PRM), preferably a PRM that comprises from 3 to 34 carbon atoms, wherein the perfume raw material from which the residue is derived comprises an aldehyde moiety, a ketone moiety, or a combination thereof, preferably wherein IV is independently selected from a monovalent organic moiety, and preferably wherein is R4 is independently selected from the group consisting of hydrogen and a monovalent organic moiety, optionally, wherein a second moiety selected from R1, one or more monovalent substituents of J, combinations thereof is replaced with a second link to an X group, preferably forming a second ring structure.
J. The treatment composition according to any of paragraphs A-I, wherein each Z is a monovalent or divalent five-membered heterocyclic moiety derivable by the removal from Formula IV of a moiety selected from R1, one or more monovalent substituents of J, or combinations thereof, wherein formula IV has the following structure:
G
R3 R4 Formula W, wherein G, le, and R4 are as described above, preferably wherein G is oxygen, and wherein each J is independently C(R2)2, wherein R2 is as described above, optionally, wherein a second moiety selected from R1, one or more monovalent substituents of J, or a combination thereof is replaced with a second link to an X group, preferably forming a second ring structure.
K. The treatment composition according to any of paragraphs I or J, wherein each Z is a monovalent or divalent heterocyclic moiety, preferably a five-membered heterocyclic moiety, derivable by the removal from Formula III or from Formula IV of a moiety selected from one or more monovalent substituents of J, preferably wherein R1 is H.
L. The treatment composition according to any of paragraphs A-K, wherein the pro-fragrance silicone polymer has the following structure:

[115116R7SiO1I2](q+2r+2) [R8R9Si02/2], [R16SiO3/2]4[SiO4/2]r Formula V
wherein: q is an integer from 0 to 150, p is an integer from 0 to 1500, r is an integer from 0 to 150, wherein q+p+r equals an integer greater than or equal to 1; each of R5, R6, R7, R8, R9 and RI moiety is independently selected from the group consisting of H, OH, a monovalent organic moiety, a radical according to Formula I, or a radical according to Formula II, wherein at least one of the R5-R16 moieties is a radical according to Formula I or a radical according to Formula II, preferably a radical according to Formula I.
M. The treatment composition according to any of paragraphs A-L, wherein the pro-fragrance silicone polymer is present at a level of from about 0.01% to about 99.9%, by weight of the treatment composition, preferably from about 0.01% to about 50%, more preferably from about 0.01% to about 25%, more preferably from about 0.1% to about 10%, more preferably from about 0.1% to about 5%, more preferably from about 1% to about 5%, by weight of the treatment composition.
N. The treatment composition according to any of paragraphs A-M, wherein the treatment adjunct is selected from the group consisting of an amine, a surfactant system, a water-binding agent, a sulfite, fatty acids and/or salts thereof, enzymes, encapsulated benefit agents, soil release polymers, hueing agents, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzyme stabilizers, catalytic materials, bleaching agents, bleach catalysts, bleach activators, polymeric dispersing agents, soil removal/anti-redeposition agents, polymeric dispersing agents, polymeric grease cleaning agents, brighteners, suds suppressors, dyes, free perfume, structure elasticizing agents, conditioning or softening agents, carriers, fillers, hydrotropes, organic solvents, anti-malodor agent, anti-microbial agents and/or preservatives, neutralizers and/or pH adjusting agents, processing aids, fillers, rheology modifiers or structurants, opacifiers, pearlescent agents, pigments, anti-corrosion and/or anti-tarnishing agents, and mixtures thereof, preferably wherein the treatment adjunct comprises a surfactant system, conditioning or softening agents, or a mixture thereof, more preferably wherein the surfactant system, if present, comprises anionic surfactant, nonionic surfactant, cationic surfactant, and/or zwitterionic surfactant, and/or more preferably wherein the conditioning or softening agents, if present, comprise a quaternary ammonium compound, silicone compounds, or both.

0. A treatment composition according to any of paragraphs A-N, wherein the treatment composition is characterized by a pH level of from about 2 to about 12, preferably from about 2 to about 8.5, more preferably from about 2 to about 7, more preferably from about 2 to about 5, more preferably from about 2 to about 4, even more preferably a pH from about 2 to about 3.5, wherein pH is determined by dissolving/dispersing the treatment composition in deionized water to form a solution at 10% concentration, at about 20 C.
P. A treatment composition according to any of paragraphs A-0, wherein the treatment composition further comprises water, preferably from about 1% to about 99%, preferably from about 5% to about 98%, or from about 10% to about 95%, or from about 50% to about 95%, or from about 60% to about 95%, or from about 75% to about 95%, by weight of the treatment composition, of water.
Q. The treatment composition according to any of paragraphs A-P, wherein the treatment composition is in the form of a liquid composition, a granular composition, a single-compartment pouch, a multi-compartment pouch, a dissolvable sheet, a particulate form where individual particles have a mass of from about lmg to about 1 gram, a fibrous article, a tablet, a bar, a flake, a non-woven sheet, or a mixture thereof, preferably in the form of a liquid composition, a particulate form where individual particles have a mass of from about lmg to about 1 gram, or mixtures thereof.
R. A treatment composition according to any of paragraphs A-Q, wherein the treatment composition is in the form of a liquid, preferably a liquid having a viscosity of from 1 to 1500 centipoises (1-1500 mPa*s), from 100 to 1000 centipoises (100-1000 mPa*s), or from 200 to 500 centipoises (200-500 mPa*s) at 20 s-1 and 21 C.
S. A liquid premix composition comprising: (a) a pro-fragrance silicone polymer as described in any of paragraphs A-L, optionally, further comprising one or more free perfume raw material; or (b) a precursor silicone polymer, and a perfume raw material that comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and a combination thereof, wherein the precursor silicone polymer and the perfume raw material are capable of condensing to form the pro-fragrance silicone polymer as described in any of paragraphs A-L; or (c) a mixture thereof.

T. The liquid premix composition according to paragraph S, wherein the liquid premix composition further comprises from about 1% to about 90%, or from about 1% to about 75%, or from about 1% to about 60%, or from about 1% to about 50%, or from about 5% to about 50%, or from about 5% to about 25%, or from about 5% to about 15%, or from about 5%
to about 10%, by weight of the composition, of water.
U. The liquid premix composition according to any of paragraphs S or T, wherein the liquid premix composition is in the form of an oil-in-water emulsion, preferably comprising droplets characterized by a volume-weighted average particle size of from about 100 nm to about 100 gm, more preferably from 1 gm to 10 gm, even more preferably from 1 gm to 5 gm.
V. The liquid premix composition according to any of paragraphs S-U, wherein, by weight of the liquid premix composition, the precursor silicone polymer is present at a level of from about 1% to about 99%, preferably from about 80% to about 10%, or from about 75% to about 20%, or from about 60% to 40%, and the perfume raw material is present at a level of from about 1% to 50%, preferably from about 5% to about 50%, or from about 5% to about 40%, or from about 5% to about 30%, or from about 5% to about 20%, or from about 5% to about 15%, or from about 5% to about 10%, preferably wherein the weight ratio of the precursor silicone polymer and the perfume raw material is from about 99:1 to about 1:1, preferably from about 50:1 to about 2:1, more preferably from about 10:1 to about 5:1.
W. The liquid premix composition according to any of paragraphs S-V, wherein the liquid premix composition further comprises an emulsifier, preferably an emulsifier selected from linear nonionic surfactant, or a branched nonionic surfactant or mixtures thereof, more preferably an emulsifier present in an amount of from about 1% to about 10%, by weight of the liquid premix composition.
X. The liquid premix composition according to any of paragraphs S-W, wherein the precursor silicone polymer comprises at least one radical selected from the group consisting of Formula VI, Formula VII, and mixtures thereof, wherein the radicals of Formula VI and Formula VII have the following structures:
(Si) ¨ X ¨ Y Formula VI;
(Si) ¨ X ¨ (Y ¨ X), ¨ (Si) Formula VII;

wherein "(Si) ¨" is the bond to an Si atom; wherein the index n is 1 or 2, preferably 1; wherein each X group is covalently linked to "(Si)" via a Si-C bond and is an independently selected divalent organic group comprising from two to twenty-four chain atoms; and wherein each Y is independently a monovalent or divalent moiety derivable by the removal from Formula VIII of a 5 moiety selected from R1, one or more monovalent substituents from J, or combinations thereof, wherein Formula VIII has the following structure:

H
Formula VIII, wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen; wherein the index m is from 2 to 4, preferably m is from 2 to 3, more preferably m is 2; wherein R1 is 10 selected from H or a monovalent moiety with a molecular weight between 15 and 500 Da, more preferably R1 is selected from H or a monovalent moiety with a molecular weight between 15 and 101 Da, even more preferably R1 is H; wherein each J is independently selected from the group consisting of C(R2)2, -0-, -N(R2)-, wherein each R2 is independently selected from the group consisting of H and a monovalent moiety with a molecular weight between 14 and 990 Da, more 15 preferably each R2 is independently selected from the group consisting of H and a monovalent moiety with a molecular weight between 14 and 186 Da, even more preferably each R2 is H, with the proviso that a first unit and a second unit can optionally be taken together, where feasible, as a divalent substituent, where the first unit is a first R2 group, and where the second unit is selected from the group consisting of a second R2 group, the R1 group, and a monovalent 20 substituent of the R1 group, preferably where the divalent substituent is selected from the group consisting of a fused ring, a spirocyclic ring, an unsaturated substituent, ¨N(R1), -C(0)-, and -C(S)-, optionally, wherein a second moiety selected from R1, one or more monovalent sub stituents of J, combinations thereof is replaced with a second link to an X group, preferably forming a second ring structure.
2.5 Y. The liquid premix composition according to any of paragraphs S-X, wherein the precursor silicone polymer is characterized by at least one of the following:
(a) a viscosity comprised in the range between 0.004 (Pa*s) and 100 (Pa*s); and/or (b) a weight average molecular weight of from about 450 Da to about 200000 Da.

Z. The liquid premix composition according to any of paragraphs S-Y, wherein the liquid premix composition further comprises an aminofunctional material, preferably where the aminofunctional material is characterized by a molecular weight of about 40 to about 1000 Daltons, more preferably from about 50 to 800 Daltons, even more preferably from about 60 to about 600 Daltons, even more preferably from about 60 to about 500 Daltons.
AA. A method of making a treatment composition, the method comprising the steps of:
providing a base composition, wherein the base composition comprises a treatment adjunct;
combining the base composition with one or more of the following: a) a pro-fragrance silicone polymer as described in any of paragraphs A-L; b) a precursor silicone polymer as described in any of paragraphs S-Z, and a perfume raw material that comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and a combination thereof, preferably wherein the precursor silicone polymer and the perfume raw material are provided together as a liquid premix composition, preferably a liquid premix composition in the form of an emulsion; or c) a mixture thereof.
BB. A method of treating a surface or article, the method comprising contacting the surface or article with a treatment composition according any of paragraphs A-R, optionally in the presence of water.
CC. An article, preferably a fabric article, comprising a surface, wherein the surface comprises the pro-fragrance silicone polymer as described in any of paragraphs A-L.
DD. A pro-fragrance silicone as described in any of paragraphs A-L.
EE. Use of a pro-fragrance silicone polymer according to paragraph DD as a perfuming agent, optionally on a surface, preferably on a fabric, optionally being formulated in a treatment composition, where the treatment composition may be a treatment composition according to any of claims A-R.
FF. A precursor silicone polymer as described in any of claims S-Z, preferably wherein when G is oxygen and when Y is derivable from the removal of R', m is not 2 or 3.
TEST METHODS
Preparation of a Pro-Fragrance Silicone Polymer Premix Emulsion A pro-fragrance silicone polymer premix emulsion may be prepared as follows.

Starting with 60.0 parts by weight of the siloxane precursor compound, add Surfonic L24-9 (2.0 parts; ex Huntsman Holland BV) and lergitolTM 15-S-40 (2.5 parts; ex The Dow Chemical Company). The mixture is mixed for 1 minute with an IKA RW 20 at 800 rpm.
Water (35.5 parts in total) is added in two equal, separate additions; after each water addition, the mixture mixed with the IKA RW 20 for approximately 10-15 min.
Perfume raw material, added in an approximately equal molar equivalent to the molar amount of radicals present according to Formulas VI and/or VII in the precursor silicone polymer, is added to the emulsion and stirred for 15 minutes with an IKA RW 20 at 275 rpm.
As an illustrative example, 93.5 parts by weight of a silicone fluid as disclosed in Synthesis Example 1 below, emulsified as described above, is combined with 6.5 parts of a perfume raw material (e.g., cinnamic aldehyde).
Preparation of a Test Fabric Enhancer/Softener Composition To an 7.5 wt % N,N di(tallowoyloxyethyl)-N,N dimethylammonium chloride in water mixture, a pro-fragrance silicone polymer premix emulsion (or neat perfume oil) is added in an amount such that the concentration of the perfume raw material or perfume raw material fragment in the fabric softener is about 0.3 wt % after the fabric softener preparation. The mixture is stirred for 5 min with an IKA RW 20 D Si Mixer, Model RW2ODS1, and IKA R1 342 impeller blade at 350 rpm. A structurant and a deposition aid is added, and the mixture is stirred for 10 min. Water is added if needed to standardize the concentration of N,N
di(tallowoyloxyethyl)-N,N
dimethylammonium chloride amongst test legs to 7.3 wt %, and the mixture stirred for 5 min. The pH is adjusted to 2-3 with in HCl, if necessary.
Preparation of a Test Pastille Composition To a 93.88 wt% molten PEG-8000 material in a speed mixer cup is added 6.12%
the pro-fragrance silicone premix emulsion of Synthetic Example 6. The speed mixer cup is quickly placed in a Flacktek DA150.FVZ-K speed mixer for lmin at 3,500 rpm. Sample pastilles were immediately made from the mixture by pouring into blue siliconized rubber molds that were preequilibrated to 4 C and spread with a 10" plastic taping knife. The pastilles were cooled at room temperature for approximately 30 min, then the pastilles were removed from the mold and stored under ambient conditions.

Fabric Preparation Method To prepare fabrics for Headspace analysis testing, fabric samples (100% Cotton Terry Cloth, Item Number ITL 1022-15PGP, CalderonTextiles, Inc. 6131 W. 80tA St., Indianapolis, Ind.
46278, Desized and conditioned with 3 wash cycles of Detergent and Fabric Softener) are treated with the Fabric Softener formulas in a manner consistent with North American consumers via clothes mini-washing machines, full scale machines, and clothes dryers. Fabric is equilibrated at 21.1 C. and 50% Relative Humidity for 24 hours prior to Headspace GCMS
analysis (see methods below). Ballast loads are comprised of cotton and polycotton knit swatches approximately 20x20 inches (50x50cm) in size.
Wash Treatment Conditions In the pastille composition performance tests below, the fabrics are treated with the following wash treatment conditions: North America Kenmore 600 Series top-loading washing machines are used. Each machine is set to run a Normal single cycle including a 12-minute wash agitation period, and 1 three-minute rinse. The water used is 137 ppm hardness and 30.6 C for the wash, and 15.5 C for the rinse. The water volume at each step is 64 Liters.
The total fabric load weight is 3.6 kg (which included 32 test fabric hand towel terry cloths, 9 of 100% cotton ballast, and about 5 of 50/50 polycotton ballast). The detergent used is TIDE Original Scent liquid without perfume (produced by The Procter & Gamble Company). Detergent is dosed at 81 g into the wash water while the wash water is filling. After the detergent is added, 25 g of the pastilles being evaluated are also added, followed by the fabric load. After the water fill is complete, the machine enters the agitation period. This is followed by the wash agitation (Normal setting), and the rinse step (with corresponding spin cycle). After the wash process is completed, the fabrics are removed.
The test fabrics are machine dried in Kenmore driers on Cotton/High setting, for 50 minutes. The test fabrics are then equilibrated for 24 hours in a 21.1 C/ 50% relative humidity controlled room.
In the fabric enhancer/softener compositions performance tests below, the fabrics are treated with the following wash treatment conditions: Wash: 12 min agitation, 30.6 C. Rinse: 2 mm agitation, 15.5 C. Water Hardness: 137 ppm. Water: 7.6 pH. Fabric Load Weight: 290 g.
Tumble Dry Setting: 50 mm High, Cotton. Detergent Dose: 9.65 g. Fabric Softener Dose: 5.71 g.
Headspace Analysis Above Fabrics To determine the level of perfume raw material in the headspace above a fabric, the following procedure is used.

The following equipment is used: Gas Chromatograph 789013 equipped with a Mass Selective Detector (597713) (MSD) and Chemstation quantitation package;
Gerstel Multi-Purpose sampler equipped with a solid phase micro-extraction (SPME) probe or similar system;
Divinylbenzene/Carboxen/Polydimethylsiloxane SPME fiber from Supleco part #57298-U (or similar fiber); 30 mx0.25 mm nominal diameter, 0.25 m film thickness, J&W 122-5532UI DB-5;
20 mL headspace vials.
To prepare the fabric for analysis, cut three 2.54 cm x 5.08 cm cotton swatches from the cotton terry that is prepared and treated according to the above methods.
Place each piece in a 20 mL headspace vial and cap.
The Gerstel auto sampler parameters are as follows: SPME¨from Incubator;
Incubation Temperature¨ 65 C.; Incubation Time-10.00 min SAMPLE PARAMETERS; Vial Penetration-22.00 mm; Extraction Time-5. 00 min; mi. Penetration-54.00 mm;
Desorption Time¨ 300 s. The GC oven parameters are as follows for the Front SS Inlet He:
Mode¨Splitless;
Heater-270 C.; GC Run Time-14.28 min. For the Oven: Initial temp.-40 C.;
Hold Time-0.5 min; Heating Program¨Rate of 17 C./min, Temp of 270 C., Hold Time of 0.25 min. The MSD parameters are as follows: Run in scan mode with a minimum range of 35 to 350 m/z;
Calibration curves are generated from the standards perfume material.
Chemstation software (or similar quantitation software) calculates the mass amount in the headspace using the calibration curve for each perfume component.
Color Change of a Composition A premix (e.g., a premix emulsion) or treatment composition may be tested for color changes according to the following procedure. The reflectance spectra and color measurements, including L*, a*, and b* were made using the LabScan XE reflectance spectrophotometer (HunterLabs, Reston, VA; D65 illumination, 10 observer, UV light excluded).
L*, a* and b*
values for premix emulsions and treatment compositions are measured at time t ¨ 0 and 14 days after mixing in the PRM. The total color change (AE) of a premix emulsion or treatment composition is calculated based on the data collected at each time point t using the following equation:
AEt = [(L*c - L* s)2 + (a*c ¨ a* s)2 + (b*c ¨ b* 02] 1/2 wherein the subscripts c and s respectively refer to the control, i.e., the premix emulsion or treatment composition with nil PRM, and the sample, i.e., the premix emulsion or treatment composition with respective aldehyde/ketone PRM, where the values used to calculate AE t are those at the corresponding time points t (0, 14 days). The desired PRM is slowly added to a sample 5 of described functionalized silicones (for example, in relative amounts sufficient to provide 1:1 molar equivalence of amine groups in the silicone to aldehyde or ketone groups of the perfume) in ajar with overhead mixing with a fourblade IKA RW 20 impeller and gently mixed for 15 minutes.
The premix emulsion mixture or treatment composition is placed into a 50 mL
(25 cm2) CELLSTAR cell culture flask with standard screw cap. At t= 0 and after 14 days at room 10 temperature, color appearance of each premix emulsion or treatment composition sample is measured on a LabScan XE 10 reflectance spectrophotometer (HunterLabs, Reston, VA; D65 illumination, 100 observer, UV light excluded).
Determination of Amine Content and % Nitrogen Total amine content, primary amine content, and/or % nitrogen of an aminofunctional IS silicone is determined according to the following method. More specifically, this method is used to determine the primary, secondary and tertiary amine values (meq/g) which are defined as the milliequivalents of amine functionality (primary, secondary and tertiary) present in one gram of a sample.
The method is based on compendia! method ASTM D2074-07, which should be used to 20 supplement this method if necessary. In broad stokes, a sample is dissolved in isopropyl alcohol and is titrated to a bromophenol blue end point using a standardized HCl solution.
The following materials are used: 0.1N Hydrochloric Acid in isopropyl alcohol (CAS 7647-01-1, 67-63-0; 99.5%; ex Fisher Scientific); Isopropyl Alcohol (CAS # 67-63-0;
99%; ex EMD);
Phenyl Isothiocyanate (CAS # 103-72-0; 98%; ex Sigma Aldrich); Salicylaldehyde (CASH 90-02-25 8; 98%; ex Sigma Aldrich); Bromophenol Blue Indicator (0.1wt% solution in ethanol or isopropyl alcohol; ex. Fisher Scientific).
Each of the following titrations should be repeated a total of three times.
Furthermore, titrant volumes must be determined empirically. Titrant volumes should be between 1 and 20mL.
If titrant volumes are less than lmL, weigh more sample. If samples are more than 20mL, weigh 30 less sample. A buret such as Metrohm Dosimat 775 or equivalent may be used in the titrations.

Regarding the yellow end point of the titrations ¨ the yellow may fade back to green, but if it is a bright clear yellow, this is to be disregarded if additional 0.1N 1-IC1 does not change the original color.
A. Titration for Total Amine Content Melt the sample (typically 100% active) in a water bath if it is not already a liquid. Mix thoroughly and accurately weigh out between 0.5 grams and 1.0 grams into a 250mL Erlenmeyer flask (wide mouth; alkali resistant). Record the weight to four decimal places.
To the flask, add 50mL of isopropyl alcohol. Add 0.5mL of bromophenol blue indicator.
Titrate with 0.1N HC1 solution while swirling until it reaches the yellow end point. Record the volume of HC1 used as V1,2,3.
B. Titration for Secondary and Tertiary Amine Content Melt the sample (typically 100% active) in a water bath if it is not already a liquid. Mix thoroughly and accurately weigh out 1.0 grams into two 250 Erlenmeyer flasks.
Record the weight to four decimal places. Mark the flasks S and T, respectively. To each flask, add 50mL of isopropyl alcohol.
To flask S, add lmL of salicylaldehyde. Stir the solution (with a magnetic stir bar) for 30 minutes. Add 0.5mL of bromophenol blue indicator solution and titrate while stirring with 0.1N
HCl to a yellow end point. Record volume of HCl used as Vuo.
To flask T, add lmL of phenyl isothiocyanate. Stir the solution (with a magnetic stir bar) for 30 minutes. Add 0.5mL of bromophenol blue indicator solution and titrate while stirring with 0.1N HCl to a yellow end point. Record volume of HCl used as V3.
C. Calculations for Amine Content The variables in the calculations described below correspond to the following:
V HC1 required for titration of specimen in mL
N = normality of the HCl solution = specimen weight in grams (g) meq/g : milliequivalents/gram Total : Total Amine Value AS : Amine value of the secondary and tertiary amine groups TA : Tertiary Amine Value Based on the measurements obtained related to the above titrations, the following calculations are used to determine the various amine contents.
Total Amine Value (Total) = (V1.2,3 * N) (meq/g) Secondary and Tertiary Amine Value (AS) = (V2.3 * 1\T) (meq/g) Tertiary Amine Value (TA) = (V3 * N) (meq/g) Secondary Amine Value = (AS ¨ TA) Primary Amine Value = (Total ¨ AS) D. Calculation of Nitrogen wt%
To determine the wt% of nitrogen in an aminofunctional silicone based on the amine content, use the following calculation.
The weight percentage of nitrogen in a compound can be calculated from the amine value (in meq/g) as follows:
(Amine Value / 1000) x (MW of Nitrogen) x 100 = wt% Nitrogen As an example, dimethylethanolamine has an amine value of 11.2 (in meq/g). Its weight percent of nitrogen (15.7wt%) is as follows:
(11.2/ 1000) x (14.01) x 100= 15.7 wt% nitrogen The following table (Table D) shows wt% of nitrogen and equivalent amine values.
Table D.
Wt% Nitrogen Amine Value (meq/g) 0.1 0.071 0.2 0.14 0.3 0.21 0.5 0.36 0.7 0.50 0.8 0.57 1.0 0.71 1.5 1.07 2.0 1.43 2.5 1.78 3.0 2.14 3.5 2.50 If the aminofunctional material contains nitrogen atoms that are not in the form of primary, secondary, and/or tertiary amines, the nitrogen content as a weight percent may be determined according to methods known to those having ordinary skill in the art.
E. Standard To confirm quality control of the method, a suitable standard may be run ¨ for example, dimethylethanol amine (a tertiary amine; 99.5%; available from Sigma Aldrich).
For this particular amine, total amine and tertiary amine content should be 11.2 0.2meq/g.
Primary and Secondary amine content should be <0.1meq/g.
Particle/Droplet Size The droplet sizes for the siloxane compounds are analyzed as the premix emulsion and in the fabric softener utilizing a Horiba, Partica, Laser Scattering, Particle Size Distribution Analyzer LA-950V2 with a static quartz cell and operated in accordance with the manufacturer's instructions.
HLB Value of Nonionic Surfactants Nonionic surfactants can be classified by the balance between the hydrophilic and lipophilic moieties in the surfactant molecule. The hydrophile-lipophile balance (HLB) scale devised by Griffin in 1949 is a scale from 0 - 20 (20 being Hydrophilic) used to characterize the nature of surfactants. The HLB of a surfactant may be calculated as follows:
JJLB = 20 M h where Mh is the molecular of the hydrophilic portion of the molecule, and M is the molecular mass of the whole molecule, giving a result on a scale of 0 to 20. An HLB value of 0 corresponds to a completely lipophilic/hydrophobic molecule, and a value of 20 corresponds to a completely hydrophilic/lipophobie molecule. See Griffin, W. C. Calculation of HLB values of Nonionic Surfactants, J. Soc. Cosmet. Chem. 1954, 5, 249-256. The HLB values for commonly-used surfactants are readily available in the literature (e.g., 1-ILA Index in McCutcheon's Emulsifiers and Detergents, MC Publishing Co., 2004). The HLB value for a mixture of surfactants can be calculated as a weighted average of the HLB values of the surfactants.

Viscosity Test Method for Silicones A preliminary estimate of the sample viscosity at 25 C is used to select the appropriate instrument geometry to be used during the final viscosity measurement analyses, which are conducted on a model AR-G2 Rheometer (manufactured by TA Instruments Corp., New Castle, Delaware, USA). A preliminary estimate of the sample viscosity may be obtained by using a Brookfield Viscometer (Brookfield Engineering Laboratories Inc., Middleboro, Massachusetts, USA). The selection of geometry for use on the AR-G2 Rheometer is determined in accordance with the following table, Table E:
Table E. AR-G2 Geometry Selection.
Preliminary Estimate of AR-G2 Geometry and Plate Size Sample Viscosity > 1000 Pa*s 25 mm parallel plate 1 to 1000 Pa*s 40 mm parallel plate > Water-thin to < 1 Pa*s 60 mm parallel plate Water-thin Couette / Cup and Bob The geometry is attached to the instrument, the instrument is mapped, the gap distance is zeroed, and the instrument temperature is set to 25 C. The measurement mode is selected as Stiff Mode when using parallel plates, or to Soft mode when using the couett cup and bob geometry.
Sample material is mounted into the sample holding geometry e.g., the base plate. The minimum gap distance allowable between the base plate and the selected geometry is 10x the diameter of the largest common particle present in sample. If there are common particles in the sample which have a diameter greater than 100 m (as determined microscopically), then the gap value is set to 10x the diameter of the largest common particle, otherwise the gap distance is set to the default value of 1000 inn (i.e. 1 mm). The selected geometry is lowered to the appropriate gap and a plastic tool is used to trim off any excess sample material. The sample material is allowed to equilibrate to the temperature of the instrument. Three rheological measurement analyses are conducted, namely:
Flow Curve, Stress Sweep, and Frequency Sweep, using the following selections and settings:
Flow Curve: select Stepped Flow 0.01 to 100; 10 pts/decade; shear stress;
constant time 20;
average last 10.
Stress Sweep: set the Stress Range as 0.01 to 100 Pa; set the Frequency at 1 rad/s.

Frequency Sweep: Set the Angular Frequency Range as 0.1 to 100.
To ensure that the analysis is conducted within the Linear Viscoelastic Region set the Stress value at a third of the stress value that was present when G' started to degrade during the prior Stress Sweep analysis.
5 Molecular Weight of Silicone Samples The molecular weight of the silicone samples may be determined by size exclusion chromatography with multi-angle light scattering detection (SEC-MALS), as provided below.
The following instrumentation is used: Waters Alliance 2695 Separations Module (pump and auto-sampler) SN C055M791M equipped with a Wyatt; rEX refractive index detector SN 874-10 REX, Waters external column heater, and Wyatt Technology DAWN; Heleos II
laser photometer SN 286-H2.
The following chromatography conditions are followed: 0.025 M
tetrabutylammonium benzoate (TBAB) in toluene solution at a flow rate of 1 mL/min; Columns ¨
Waters Styragel guard column and two Waters Styragel 11R5 linear columns; refractive index detector is at 25 C'; all 15 other components are at ambient room temperature.
To prepare the samples, samples are accurately weighed into polyseal capped vials. The samples are then diluted with 3 mL of eluent (TBAB in toluene) to achieve concentration of 8.0 mg/ml. Samples are swirled by hand and gently mixed and allowed to sit overnight to ensure complete dissolution of the sample. They are then filtered via syringe filter (PALL Acrodisc 13 20 mm syringe filter with 0.2 mm nylon membrane) into auto-sampler vials.
Poly(dimethyl)siloxane (PDMS) reference material is prepared in the same manner.
The data collection and workup is performed with Astra 5.3.4.19 software (Wyatt Technology, Santa Barbara, CA). The dn/dc values of the silicone samples are calculated from peak data using Astra software.

The examples provided below are intended to be illustrative in nature and are not intended to be limiting.

Synthesis Examples The following Synthetic Examples 1-20 show the synthesis of illustrative pro-fragrance silicone polymers and their silicone precursors, according to the present disclosure. Comparative Synthetic Example A shows a comparative silicone polymer that does not include a heterocyclic moiety as provided in the present disclosure.
For consistency and illustrative/comparative purposes, each example reacts a neat silicone precursor with the same perfume raw material, cinnamic aldehyde or isocyclocitral, which have the following structures:
14111 0 o cinnamaldehyde isocyclocitral However, it is understood that other aldehyde- or ketone-containing PRMs according to the present disclosure may also lead to the formation of suitable pro-fragrance silicone polymers; some of these are exemplified and tested in the Performance Examples below. It is also understood that the Synthetic Examples may be directly formulated into a treatment composition; however, for the case of the reported performance and stability examples below, all Synthetic Examples are formulated into a treatment composition as a liquid premix emulsion as described above.
For each Synthetic Example, the silicone precursor (e.g., having the reported X-Y group) and the resulting pro-fragrance heterocyclic moiety (e.g., having the reported X-Z group) is provided below in Table F. Comparative Synthetic Example A is also shown, although it does not include a -Y moiety according to the present disclosure, nor does the resulting material include a -Z moiety according to the present disclosure.
Comparative Synthetic Example A.
Cinnamic aldehyde (0.35 g; available from Symrise, Holzminden, Germany) is added to an amino-modified silicone (A), KF-8003 (5g, available from Shin-Etsu Silicones of America Inc., Akron, OH). The mixture is stirred for 12h. The resulting clear fluid (A') is analyzed by 1HNMR.

As shown in Table F below, the resulting material of Comparative Synthetic Example A' does not include a heterocyclic moiety according to the present disclosure.
Synthetic Example 1.
Method A: An epoxy functionalized silicone, EMS-622 Fluid (60 g; available from Gelest, Morrisville, PA), is stirred with isopropyl alcohol (3 g, Sigma-Aldrich, St.
Louis, MO) in a three-neck round bottom flask. To this fluid is added butylamine (28 g; Sigma-Aldrich, St. Louis, MO).
The flask is sealed and placed under a N2 atmosphere for 48h. Excess amine was removed under reduced pressure yielding a clear fluid. The independent silicone fluid 1 appeared stable for several months by 1H NMR.
Method B: An epoxy functionalized silicone, EMS-622 Fluid (5 g; available from Gelest, Morrisville, PA), is combined with 2-Methyl-2,4-pentanediol (0.25 g, Sigma-Aldrich, St. Louis, MO) and butylamine (2.3 g; Sigma-Aldrich, St. Louis, MO) and stirred for 24h.
Excess amine was removed under reduced pressure yielding 1 as a clear fluid.
Method C: An epoxy functionalized silicone, EMS-622 Fluid (5 g; available from Gelest, Morrisville, PA), is combined with butylamine (2.3 g; Sigma-Aldrich, St.
Louis, MO) and stirred for 48h. Excess amine was removed under reduced pressure yielding 1 as a clear fluid.
Regardless of method, to a 5g fraction of the independent fluid 1 is added cinnamic aldehyde (0.5g; available from Symrise, Holzminden, Germany) which is stirred for 12h. The resulting clear fluid 1' is analyzed by 1H NMR.
Synthetic Example 2.
An epoxy functionalized silicone, EMS-622 Fluid (60 g; available from Gelest, Morrisville, PA), is combined with isopropyl alcohol (3 g, Sigma-Aldrich, St. Louis, MO) and isopropyl amine (23 g; Sigma-Aldrich, St. Louis, MO) and stirred for 24h. Excess amine was removed under reduced pressure yielding a clear fluid. The independent silicone fluid 2 appeared stable for several months by 1H NMR.
To a stirring fluid of 2 (5 g) is added cinnamic aldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12h the resulting clear fluid 2' is analyzed by 1H
NMR.

Synthetic Example 3.
An epoxy functionalized silicone, EMS-622 Fluid (60 g; available from Gelest, Morrisville, PA), is combined with isopropyl alcohol (3 g, Sigma-Aldrich, St. Louis, MO) and cyclohexylamine (38 g; Sigma-Aldrich, St. Louis, MO) and stirred for 24h. Excess amine was removed under reduced pressure yielding a light yellow fluid. The independent silicone fluid 3 appeared stable for several months by 1H NMR.
To a stirring fluid of 3 (5 g) is added cinnamic aldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12h the resulting clear fluid 3' is analyzed by 1H
NMR.
Synthetic Example 4.
An epoxy functionalized silicone, EMS-622 Fluid (10 g; available from Gelest, Morrisville, PA), is combined with isopropyl alcohol (0.5 g, Sigma-Aldrich, St. Louis, MO) and tert-butylamine (4.6 g; Sigma-Aldrich, St. Louis, MO) and stirred for 24h. Excess amine was removed under reduced pressure yielding a clear fluid. The independent silicone fluid 4 appeared stable for several months by 1H NMR.
To a stirring fluid of 4 (5 g) is added cinnamic aldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12h the resulting clear fluid 4' is analyzed by 1H
NMR.
Synthetic Example 5.
An epoxy functionalized silicone, EMS-622 Fluid (10 g; available from Gelest, Morrisville, PA), is combined with isopropyl alcohol (0.5 g, Sigma-Aldrich, St. Louis, MO) and methyl amine (2.0 g; Sigma-Aldrich, St. Louis, MO), the flask is sealed and stirred for 24h. Excess amine was removed under reduced pressure yielding 5 as clear fluid.
To a stirring fluid of 5 (5 g) is added cinnamic aldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12h the resulting in the clear fluid 5' is analyzed by 11-1-NMR.
Synthetic Example 6.
Method A: An epoxy functionalized silicone, EMS-622 Fluid (45 g; available from Gelest, Morrisville, PA), is combined with NH3 (50 ml, 2M IPA solution, Sigma-Aldrich, St. Louis, MO) in a round bottom flask. The flask is sealed and stirred at room temperature for 72h. Excess amine was removed under reduced pressure yielding a clear fluid. The independent silicone fluid 6 appeared stable for several months by 1H NMR.
Method B: An epoxy functionalized silicone, EMS-622 Fluid (10 g; available from Gelest, Morrisville, PA), is combined with isopropyl alcohol (0.5 g, Sigma-Aldrich, St. Louis, MO) to which NH3 is bubbled through the fluid for 12h (2.0 g; Sigma-Aldrich, St.
Louis, MO), the flask is then sealed and stirred for an additional 24h. Excess amine was removed under reduced pressure yielding 6 as clear fluid.
To a stirring fluid of 6 (5 g) is added cinnamic aldehyde (0.55 g; available from Symrise, Holzminden, Germany). After 12h the resulting clear fluid 6' is analyzed by 111 NMR.
Synthetic Example 7.
An epoxy functionalized silicone, X-22-343 (15 g; available from Shin-Etsu Silicones of America Inc., Akron, OH), is combined with 2-Methyl-2,4-pentanediol (0.95 g, Sigma-Aldrich, St. Louis, MO) and octylamine (4.0 g; Sigma-Aldrich, St. Louis, MO) and stirred via overhead stirrer at 800rpm for 16h. The independent silicone fluid 7 appeared stable for several months by 1H NMR.
To a stirring fluid of 7 (5 g) is added cinnamic aldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12h the resulting clear fluid 7' is analyzed by NMR.
Synthetic Examples 8.
An amino-modified silicone, KF-8003 (500 g; available from Shin-Etsu Silicones of America Inc., Akron, OH), is combined with 2-Methyl-2,4-pentanediol (26g, Sigma-Aldrich, St.
Louis, MO) in a three-neck round bottom flask. The solution is stirred until homogenous and placed under a N2 atmosphere. To this solution is added 1,2-Propylene oxide (18.15 g;
Sigma-Aldrich, St.
Louis, MO) and the mixture is stirred at 80 C for 48h. The independent fluid 8 appears stable for several months by 1H NMR.
To a 5g fraction of the independent fluid 8 is added cinnamic aldehyde (0.32 g; available from Symrise, Holzminden, Germany) which is stirred for 12h. The resulting clear fluid 8' is analyzed by 1H NMR.

Synthetic Example 9.
An amino-modified silicone, KF-8003 (500 g; available from Shin-Etsu Silicones of America Inc., Akron, OH), is combined with 2-Methyl-2,4-pentanediol (27g, Sigma-Aldrich, St.
Louis, MO) in a three-neck round bottom flask. The solution is stirred until homogenous and placed 5 under a N2 atmosphere. To this solution is added butyl glycidyl ether (40.7 g; Sigma-Aldrich, St.
Louis, MO) and the mixture is stirred at 80 C for 48h. The independent fluid 9 appears stable for several months by 114 NMR.
To a 5g fraction of the independent fluid 9 is added 2,4,6-trimethylcyclohex-3-ene- 1-carbaldehyde (0.35 g; available from IFF, New York, NY) which is stirred for 12h. The resulting 10 clear fluid 9' is analyzed by 111 NMR.
Synthetic Example 10.
An amino-modified silicone, KF-8003 (100 g; available from Shin-Etsu Silicones of America Inc., Akron, OH), is combined with 2-Methyl-2,4-pentanediol (5.5 g, Sigma-Aldrich, St.
Louis, MO) in a three-neck round bottom flask. The solution is stirred until homogenous and placed 15 under a N2 atmosphere. To this solution is added cyclohexene sulfide (8.9 g; Sigma-Aldrich, St.
Louis, MO) and the mixture is stirred at 80 C for 48h. The independent fluid 10 appears stable for months in a sealed container by NMR.
To a 5g fraction of 10 the independent fluid above is added cinnamic aldehyde (0.31 g;
available from Symrise, Holzminden, Germany) which is stirred for 12h. The resulting light-yellow 20 fluid 10' is analyzed by 114 NMR.
Synthetic Example 11.
An amino-modified silicone, AMS-152 (100 g; available from Shin-Etsu Silicones of America Inc., Akron, OH), is combined with 2-Methyl-2,4-pentanediol (10.5 g, Sigma-Aldrich, St. Louis, MO) in a three-neck round bottom flask. The solution is stirred until homogenous and 25 placed under a N2 atmosphere. To this solution is added ethylene sulfide (4.25 g; Sigma-Aldrich, St. Louis, MO) and the mixture is stirred at 50 C for 48h. The independent fluid 11 appears stable for months in a sealed container by 11-I NMR.

To a 5g fraction of the independent fluid 11 is added cinnamic aldehyde (0.35 g; available from Symrise, Holzminden, Germany) which is stirred for 12h. The resulting light-yellow fluid 11' is analyzed by 1H NMR.
Synthetic Example 12.
An epoxy functionalized silicone, XF-22-343 (50 g; available from Shin-Etsu Silicones of America Inc., Akron, OH), is stirred with 1,2-hexanediol (7 g, Sigma-Aldrich, St. Louis, MO) in a three-neck round bottom flask. To this fluid is added isomeric mixture of a cyclic diamine Baxxodur (98 g; BASF, Ludwigshafen, Germany). The flask is sealed and placed under a N2 atmosphere for 24h. Excess amine was removed under reduced pressure yielding a light-yellow fluid. The independent silicone fluid 12 darkened upon standing over several months.
To a 5g fraction of freshly prepared independent fluid 12 is added cinnamic aldehyde (2.15 g; available from Symrise, Holzminden, Germany) which is stirred for 12h. The resulting light-yellow fluid 12' is analyzed by 1H NMR.
Synthetic Example 13.
An epoxy functionalized silicone, XF-22-343 (50 g; available from Shin-Etsu Silicones of America Inc., Akron, OH), is stirred with 1,2-hexanediol (2.8 g, Sigma-Aldrich, St. Louis, MO) in a three-neck round bottom flask. To this fluid is added isomeric mixture of a cyclic diamine Baxxodur (6.7 g; BASF, Ludwigshafen, Germany). The flask is sealed and placed under a N2 atmosphere for 24h. The independent fluid 13 appears stable for months in a sealed container by 1H NMR.
To a 5g fraction of freshly prepared independent fluid 13 is added cinnamic aldehyde (2.15 g; available from Symrise, Holzminden, Germany) which is stirred for 12h. The resulting fluid 13' is analyzed by Ili NMR.
Synthetic Example 14.
An epoxy functionalized silicone, XF-22-343 (100 g; available from Shin-Etsu Silicones of America Inc., Akron, OH), is stirred with 1,2-hexanediol (8.5 g; Sigma-Aldrich, St. Louis, MO) in a three-neck round bottom flask. To this fluid is added ethylene diamine (71 g; Sigma-Aldrich, St. Louis, MO). The flask is placed under a N2 atmosphere and heated to 30 C
for 24h. Excess amine was removed under reduced pressure yielding 14 a light-yellow fluid.
Cross-linking is facile with ethylene diamine; therefore, excess amine is critical in the preparation of 14.
To a 5g fraction of the independent fluid 14 is added 2,4,6-trimethylcyclohex-3-ene- 1-carbaldehyde (0.35 g; available from IFF, New York, NY) which is stirred for 12h. The resulting clear fluid 14' is analyzed by 1H NMR. The predominate structural motif is oxazolidine, however, trace amounts of imine were observed.
Synthetic Example 15.
An epoxy functionalized silicone, KF-102 (50 g; available from Shin-Etsu Silicones of America Inc., Akron, OH), is combined with isopropyl alcohol (5 g, Sigma-Aldrich, St. Louis, MO) and butylamine (5 g; Sigma-Aldrich, St. Louis, MO) the flask is then placed under a N2 atmosphere. Once homogenous, the flask is heated to 30 C and stirred for 72h.
The course of the reaction is monitored by 11-INMR. Excess amine was removed under reduced pressure yielding a clear fluid. The independent silicone fluid 15 appeared stable for several months by 1H NMR.
To a stirring fluid of 15 (5 g) is added cinnamic aldehyde (0.2 g; available from Symrise, Holzminden, Germany). After 12h the resulting clear fluid 15' is analyzed by 1H NMR.
Synthetic Example 16.
An amino-modified silicone, KF-8003 (10 g; available from Shin-Etsu Silicones of America Inc., Akron, OH), is combined with 2-Methyl-2,4-pentanediol (0.5 g, Sigma-Aldrich, St.
Louis, MO) in a three-neck round bottom flask. The solution is stirred until homogenous and placed under a N2 atmosphere. To this solution is added methyl glycolate (0.6 g;
Sigma-Aldrich, St. Louis, MO) and the mixture is stirred at 120 C for 48h. The resulting fluid 16 appears stable for several months by 1H NMR.
To a 5g fraction of the fluid 16 is added cinnamic aldehyde (0.34 g; available from Symrise, Holzminden, Germany) which is stirred at 50 C for 12h. The resulting fluid 16' is analyzed by 1H
NMR.
Synthetic Example 17.
An acrylate functionalized silicone, UMS-182 fluid (50 g; available from Gelest, Morrisville, PA), is combined with ethanolamine (6.25 g; Sigma-Aldrich, St.
Louis, MO) and placed under a N2 atmosphere. The mixture is stirred at room temperature until the reaction is complete, monitored by 1H NMR. The independent fluid 17 appears stable for months in a sealed container by 1H NMR.
To a 5g fraction of the independent fluid 17 is added cinnamic aldehyde (1.25 g; available from Symrise, Holzminden, Germany) which is stirred for 12h. The resulting clear fluid 17' was analyzed by 'NMR.
Synthetic Example 18.
An amino-modified silicone, DMS-A15 (10 g; available from Gelest, Morrisville, PA), is combined with isopropyl alcohol (5 g, Sigma-Aldrich, St. Louis, MO) and 1,4-Butanediol diglycidyl ether (10 g; Sigma-Aldrich, St. Louis, MO) the flask is then placed under a N2 atmosphere. Once homogenous, the flask is heated to 30 C and stirred for 72h.
The course of the reaction is monitored by 11-1 NMR. Excess oxirane was removed under reduced pressure yielding a clear fluid. The independent silicone fluid 18 appeared stable for several months by 1H NMR.
To a stirring fluid of 18 (5 g) is added cinnamic aldehyde (0.4 g; available from Symrise, Holzminden, Germany). After 12h the resulting clear fluid 18' is analyzed by 1H NMR.
Synthetic Example 19.
A halogenated-modified silicone, LMS-152 fluid (10 g; available from Gelest, Morrisville, PA), is combined with ethanolamine (6.25 g; Sigma-Aldrich, St. Louis, MO) and placed under a N2 atmosphere. The mixture is stirred at 30 C until the reaction is complete monitored by 1H NMR.
The independent fluid 19 appears stable for months in a sealed container by 1H
NMR.
To a 5g fraction of the independent fluid 19 is added cinnamic aldehyde (1.25 g; available from Symrise, Holzminden, Germany) which is stirred for 12h. The resulting fluid 19' was analyzed by Ili NMR.
Synthetic Example 20.
An epoxy functionalized silicone, EMS-622 fluid (10 g; available from Gelest, Morrisville, PA), is combined with isopropyl alcohol (0.5 g, Sigma-Aldrich, St. Louis, MO), butylamine (2.5 g; Sigma-Aldrich, St. Louis, MO), propylamine (2.2 g; Sigma-Aldrich, St.
Louis, MO) and stirred for 48h. Excess amine was removed under reduced pressure yielding a clear fluid. The independent silicone fluid 20 appeared stable for several months by 1H NMR.
To a stirring fluid of 20 (5 g) is added cinnamic aldehyde (0.5 g; available from Symrise, Holzminden, Germany). After 12h the resulting clear fluid 20' is analyzed by 1H NMR.
Structures of the Synthetic Examples.
Table F below shows the X-Y and the X-Z structures of the Synthetic Examples described above. The X-Y column shows, for example, the (Si)-X-Y moiety, etc., of the precursor silicone polymer, e.g., the radical according to Formula VI or Formula VII; in the above examples are labeled with a number, e.g., 1. The X-Z column shows, for example, the (Si)-X-Z moiety, etc., of the pro-fragrance silicone polymer, e.g., the radical according to Formula I
or Formula II; in the above Synthesis Examples, these are labeled with a number having a "prime"
notation, e.g., 1'.
Table F also includes Comparative Synthetic Example A (and A'), which does not include (Si)-X-Y or (Si)-X-Z radicals as described in the present disclosure (e.g., no heterocyclic ring is formed), but they are included in the table for convenience / comparative purposes. This comparative example is marked with an asterisk (*).
Table F. Structural representation of the Synthesis Examples Illustrative X-Y moiety Illustrative X-Z
moiety No. (e.g., of precursor silicone polymer No.' (e.g., of pro-fragrance silicone polymer according to Formula VI or VII) according to Formula I or II) (Si) (Si) A* A' *

(Si) (Si) 1 1' 0 NH N\
b4H9 b4H9 (Si) (Si) L.

2 2' L.,c0H L...c.0 \ .
NH N
)-- )--(Si) (Si) ...

3 Lt.OH 3' Lo \ .NH N
b b (Si) (si) L. 1,...
,0 0 4 L 4'i.OH Li..0 \ =Nyz___ Nv /----(Si) (Si) 5 o LI L.
5 ' 0 LIOH LIO
\ =
NH N
\ \
Cs') ( Si) 0 6' Lt.o LIOH ii0 \ .

(Si) (Si) L'Io L..
-Nso 7' L.,CH L.r...0 \ =
NH N
t8H17 NC8H1 7 (Si) (Si) ---.
L.
8 8' 'teY 0 H
OH
(Si) (Si) LI
-,..
9 9' Nr0--C4F19 0 0-04H9 H

OH
(Si) (Si) LINjg 10' S
H
SH
IIP
(Si) (Si) 11 11' '1\1"Th H-....... S
SH
.
(Si) L..
(Si) Li. -...o \ *N
1....,c0H
12 12' 1\l'R
NH
H2N'il \

(Si) L-..
(Sit -.o \ _NH li.0 N \ =
13 13' r_cNH \r-\1\1 r0 OH
/
(SOI
=
(Si) (so L...
"1...o ,o 14 1...,,(OH 14' Li.0 .
NH N
1) (Si (Si 15 15' -.., NH

Y
4H9 c4H9 (Si) (Si) LI o

16 Nit) H 16' N").
OH

(Si) (Si)

17 0 17' C-N

OH
¨
(Si)

18 (3, )--^[vi 18, (Si ( Si) ( Si)

19 NH 19' OH 1110, (Si) R = C4H9 and C3H7 (Si) R = C4H9 and

20 0 20' 0 NH N41, iR
In the above Synthesis Examples, precursor silicone polymers (or comparative silicones, such as KF-8003) and the indicated perfume raw materials are combined /
reacted to form a fluid comprising the pro-fragrance silicone polymers according to present disclosure.
In the following Performance Examples and Stability Examples, precursor silicone polymers (or comparative silicones, such as KF-8003) and the indicated perfume raw materials are made into an emulsion, substantially following a procedure aligned with the method found in the Test Methods section above ("Preparation of a Pro-Fragrance Silicone Polymer Premix Emulsion"). Despite the different methods of preparation between the Synthesis Examples and the Performance and Stability Examples, the inputs and outputs, in terms of the pro-fragrance silicone polymers, are substantially the same.

Performance Examples In Performance Examples 1-5 below, treatment compositions comprising neat perfume oil, a liquid premix emulsion comprising the precursor silicone polymers according to the present disclosure (e.g., based on alkanolamine or thiol amine silicone precursors described above) and PRMs as indicated, or premix emulsions comprising comparative silicone polymers are compared via treatment cycles in an automatic washing machine according to the Fabric Treatment methods provided above. After treatment, the fabrics are tested for Headspace Analysis according to the test methods provided above. The data below shows the benefits afforded by heterocyclic moieties, such as oxazolidine and thiazolidine motifs, in delivering benefit agents.
Performance Example 1. Benefits of pro-fragrance silicone polymers Initially, two silicone scaffolds are selected to examine perfume benefit. The first stems from traditional amino-modified silicones, which can then react with oxiranes to yield alkanolamines (Synthetic Example 8). The second is derived from epoxy silicones that form alkanolamines after nucleophilic attack from an amine (Synthetic Example 1).
To evaluate these materials, a range of perfume raw materials are examined.
In the example below, equal molar concentrations of four aldehydic perfume raw materials are provided to a premix emulsion of the respective test legs, then formulated into a Test Fabric Enhancer/Softener Composition, prepared as provided in the test methods above.
Test fabrics are prepared, wash treated, and tested for headspace analysis above the fabrics according to the test methods above.
It is understood that for the rows reading "Synthetic Example 1," etc., both in Table 1 and in subsequent tables, the sample was prepared substantially in accordance with the method and silicone precursor provided in the listed Synthetic Example, but with the perfume raw materials listed in the example (in equal molar concentrations) rather than with just cinnamic aldehyde or isocyclocitral, and formulated as a premix emulsion as detailed above.
Results of the Headspace Analysis Above Fabrics testing is provided below in Table 1.

Table 1.
Average headspace concentration of aldehyde perfume raw materials' above fabrics Compound Amount of Amount of Amount of Amount of Total Isocyclocitral Cymal Cinnamic Floralozone Headspace released released aldehyde released Amount (nmol/L) (nmol/L) released (nmol/L) (nmol/L) (nmol/L) Neat raw materials 0.01 0.30 0.04 0.15 0.51 Synthetic Example 1 5.82 2.48 0.09 3.90 12.29 Synthetic Example 8 3.57 3.18 0.49 2.43 9.67 Comp. Synthetic 2.64 0.72 0.43 3.49 7.28 Example A
"All aldehyde raw materials were combined in equal molar concentrations.
b The silicone used in Comparative Synthetic Example A (KF-8003) is a product of Shin-Etsu Silicones of America Inc., Akron, OH. The silicone premix emulsion solution of Comp.
Synthetic Sample A is prepared using substantially the same method as for the premix emulsions of Synthetic Examples 1 and 8.
As shown in Table 1, the alkanolamine silicones 1, 8, and comparative amino-modified Comparative Synthetic Example A, showed an improvement in total headspace over neat raw materials. Furthermore, the alkanolamine silicones 1 and 8 showed an increase in total headspace 5 over the amino-modified Comparative Synthetic Example A. Example fluid 8, which was synthetically derived from KF-8003, had an affinity for sterically unencumbered neat raw materials versus the parent KF-8003 silicone (see Comparative Synthetic Example A) .
Fluid 1 had the highest total headspace with a more balanced reactivity toward non-allylie aldehydes.
Performance Example 2. Effect of sterie hinderance 10 This example shows the effect of stearic hinderance at the nitrogen atom of the heterocyclic moiety of the pro-fragrance silicone polymers. The tests are run substantially the same as in Performance Example 1, with the PRMs and Synthetic Examples provided below in Table 2; as with Performance Example 1, it is understood that the pro-fragrance silicone polymers are made with the listed PRMs rather than with just cinnamic aldehyde or isocyclocitral and reacted in the 15 form of a premix emulsion as detailed above.
Results of the Headspace Analysis Above Fabrics are provided in Table 2.

Table 2.
Average headspace concentration of aldehyde perfume raw materials' above fabrics Compound Amount of Amount of Amount of Amount of Total Methyl P.T.
Precyclemone Floralozone Headspace nonyl Bucinal B released released Amount acetaldehyde released (nmol/L) (nmol/L) released (nmol/L) (nmol/L) (nmol/L) Neat raw materials 5.64 7.91 4.93 0.89 19.37 Synthetic Example 1 42.90 28.42 29.42 12.98 113.72 Synthetic Example 2 17.25 17.00 6.13 1.83 42.21 Synthetic Example 3 27.65 22.57 6.30 2.06 58.58 Synthetic Example 4 9.12 10.58 5.92 1.40 27.02 a The formulation of the accord is as follows: 10 wt% Methyl nonyl acetaldehdye, 40 wt%
P.T.Bucinal, 20 wt% Precyclemone B, and 30 wt% Floralozone.
As shown in Table 2, each of the example pro-fragrance silicones delivered a higher total headspace over neat raw material. Total headspace concentration for the Synthetic Example silicones is 1 > 3 > 2 > 4. Without wishing to be bound by theory, it is believed that this trend is rationalized based on sterics, where less steric bulk at the nitrogen leads to improved total headspace ¨ e.g., n-butylamine > cyclohexylamine > iso-propylamine > tert-butylamine. The steric influence is highlighted upon examination of Synthetic Examples 2 and 3. The a-carbon to the nitrogen atom in both Synthetic Examples 2 and 3 are secondary in substitution in respect to carbon atoms; however, in Synthetic Example 3 the a-carbon is in a ring structure resulting in a smaller steric influence. This subtle difference led to a noted difference in the total quantity of delivered perfume raw materials.
Example 3. Effect of amine substitution This example shows the effect of primary vs. secondary substitution at the nitrogen atom of the heterocyclic moiety of the pro-fragrance silicone polymer. The tests are run substantially 5 the same as in Performance Example 1, with the PRMs and Synthetic Examples provided below in Table 3; as with previous examples, it is understood that the pro-fragrance silicone polymers are made with the listed PRMs rather than with just cinnamic aldehyde or isocyclocitral, and reacted in the form of a premix emulsion as detailed above.

Results of the Headspace Analysis Above Fabrics are provided in Table 3.
Table 3.
Average headspace concentration of aldehyde perfume raw materials' above fabrics Compound Amount of Amount of Amount of Amount of Total Methyl P.T.
Precyclemone Floralozone Headspace nonyl Bucinal B released released Amount acetaldehyde released (nmol/L) (nmol/L) released (nmol/L) (nmol/L) (nmol/L) Neat raw materials 1.65 3.66 0.67 0.61 6.59 Synthetic Example 1 16.22 31.49 42.22 18.27 108.20 Synthetic Example 6 4.36 18.71 16.39 12.90 52.36 a The formulation of the accord is as follows: 10 wt% Methyl nonyl acetaldehdye, 40 wt%
P.T.Bucinal, 20 wt% Precyclemone B, and 30 wt% Floralozone.
As shown in Table 3, alkanolamine silicones of Synthetic Examples 1 and 6 had an increased total headspace over neat raw material. Furthermore, Synthetic Example 1, which contained a secondary amine, resulted in a higher total headspace than the primary amine in Synthetic Example 6. Thus, alkyl substitution of the amine may be more preferred in specific applications.
Example 4. Additional examples of pro-fragrance silicone polymers This example shows additional example of pro-fragrance silicone polymers.
Synthetic 0 Example 11 contains a thiol amine in the precursor and forms a thiazolidine ring when reacted with the perfume raw material. Synthetic Example 12 forms an oxazolidine ring, but because the precursor also includes a cyclic amine in the pendant group that can also react with a perfume raw material, the pendant group may ultimately be loaded with two PRM residues.
The tests are run substantially the same as in Performance Example 1, with the PRMs and Synthetic Examples provided below in Table 4; as with previous examples, it is understood that the pro-fragrance silicone polymers are made with the listed PRMs rather than with just cinnamic aldehyde or isocyclocitral, and reacted in the form of a premix emulsion as detailed above.
Results of the Headspace Analysis Above Fabrics are provided in Table 4.

Table 4.
Average headspace concentration of aldehyde and ketone perfume raw materials' above fabrics Compound Amount Amount Amount Amount of Amount of Total of Iso of Cymal of Floralozone 8-Headspace cyclo released Cinnamic released Damascone Amount citral (nmol/L) aldehyde (nmol/L) released released released (nmol/L) (nmol/L) (nmol/L) (nmol/L) Neat raw 0.034 0.061 0.002 0.077 0.030 0.204 materials Synthetic 3.682 0.064 0.067 4.183 3.862 11.858 Example 11 Synthetic 12.429 1.419 0.313 0.938 7.073 22.172 Example 12 'All aldehyde raw materials were combined in equal molar concentrations.
Synthetic Example 11, which forms a thiazolidine ring in the presence of the raw materials, had an increase in total headspace over neat raw material through the wash (see Table 4). Fluid 11 had a strong interaction with sterically hindered aldehydes and ketones.
Oxazolidine-forming silicone 12 reacted strongly with each of the raw materials.
Example 5. Use in a particulate laundry additive In this example, the formulation of material are prepared in a dry-formed particles application (e.g., a pastille comprising polyethylene glycol as a carrier;
similar in size and shape to those sold as DOWNY UNSTOPABLESTM by The Procter & Gamble Company). The formulations of the particles for each leg are provided in Table 5A, where Synthetic Example 6 is introduced as a premix emulsion as detailed above. Amounts are provided by %
weight of the composition.
Table 5A.
Leg PEG-8000 Silicone premix Neat PRIVIs Neat raw materials" 99.34% 0.00% 0.66%
Synthetic Example 6 89.86% 10.14% 0.00%
'The cumulative raw materials equated 0.66 wt% in both legs.

In the example below, equal molar concentrations of the perfume raw materials are provided to a Test Fabric Pastille Composition, prepared as provided in the Test Methods above.
Test fabrics are prepared, wash treated, and tested for headspace analysis above the fabrics according to the Test Methods above. The performance test results are provided in Table 5B.
Table 5B.
Average headspace concentration of aldehyde and ketone perfume raw materials' above fabrics Leg Amount Amount Amount of Amount of Amount of Total of Iso of Cymal Intereleven Ligustral-1 6-Headspace cyclo released aldehyde released Damascone ( citral (nmol/L) released (nmol/L) released nmol/L) released (nmol/L) (nmol/L) (nmol/L) Neat raw 0.001 0.353 0.817 0.144 0.007 1.322 material Synthetic 0.057 0.443 4.289 0.284 0.217 5.290 Example 6 "All aldehyde raw materials were combined in equal molar concentrations.
As shown in Table 5B, the Synthetic Example 6 in a dry particles formulation showed an advantage over neat raw materials through the wash.
Stability Example In Stability Example 1, silicone premix emulsions and treatment compositions are tested for color stability upon storage.
Stability Example 1. Color stability in silicone premix Pro-perfume silicone premixes, specifically premixes in the form of emulsions, and related fabric softener products formed from such premix emulsions are prepared. Color measurements for silicone premix emulsions of Synthetic Examples 1 and 8 are provided and are measured as described in Test Methods above. Aldehyde-containing perfume raw materials (Cymal, Isocyclocitral, Cinnamic aldehyde, and Floralozone) are combined with the silicones in equal molar concentrations. As with previous examples, it is understood that the pro-fragrance silicone polymers are made with the listed PRMs rather than just cinnamic aldehyde or isocyclocitral, and reacted with the PRMs in the form of a premix emulsion as detailed above.
Comparative compositions are made with a KF-8003 silicone premix emulsion and the same PRMs.
Color stability of the premix emulsions and the fabric softener products upon storage for 5 two weeks is assessed by the Color Change of a Composition test method provided above. The results are provided in Table 6 below.
Table 6.
Average (AFL') absorption change upon storing at 20 C for 2 weeks.
Compound AF t [L*, a*, b*] AE t [Li, a*, b*]]
Premix Emulsion (a.u.) Fabric Softener Formulation Synthetic Example 1 11.5 189.3, -2.9, 10.81 15.8 [74.0, -2.4, -5.6]
Synthetic Example 8 16.3 [76.0, 9.8, 13.3] 27.2 [64.4, 1.9, 11.0]
Comp. Synthetic Example Ab 28.6 [71.0, 12.3, 17.4] .. 37.9 [54.5, 15.7, -1.9]
"AF,t is calculated as defined in test methods.
b Made with KF-8003, product of Shin-Etsu Silicones of America Inc., Akron, OH. The silicone premix emulsion solution of Comp. Synthetic Sample A is prepared using substantially the same method as for the premix emulsions of Synthetic Examples 1 and 8.
As shown in Table 6, Synthetic Examples 1 and 8, each of which forms heterocyclic moieties in combination with the PRM residues, result in lower AEt in both a premix emulsion and 10 treatment composition compared to the solutions formed from the imine-forming silicone KF-8003. Without wishing to be bound by theory, it is believed that it-bonds are likely the origin of color intensity for imines represented in Comparative Synthetic Example A. The influence of 7C-bond conjugation is further highlighted using cinnamic aldehyde, where the extended conjugation upon imine formation leads to significant coloring. Additionally or alternatively, it is believed the 15 nature of bonding in heterocycles precludes static it-bonds, resulting in Synthetic Examples 1 and 8 having improved color stability with time due to reduced conjugation and diminished gelling.
Exemplary Formulations The section provides exemplary, non-limiting formulations of premixes and treatment compositions.

Formulation Example 1. Exemplary premixes Table 7 provides exemplary fragrance premix formulations that may be incorporated into consumer products. Amounts are provided as weight percent, by weight of the premix.
Table 7.
Ingredient A
Silicone Polymerl 80 50 Aminofunctional material2 5 0 Perfume raw materials3 15 9 Emulsifier 6 Water 35 1 Precursor silicone polymer of Synthetic Example 1 2 Methyl cyclohexane diamine (Baxxodur EC210, ex BASF) 3 Contains ethyl vanillin, vanillin, heliotropin, and lilial, each selected so that each PRM is present in an amount to provide equal moles of aldehyde moieties.
Formulation Example 2. Particulate treatment composition A particulate treatment composition may be made according to the following procedure;
such compositions may be useful as laundry additive consumer products.
The Pro-Fragrance Silicone Polymer Premix Emulsion made according to the method provided in the Test Method Section, and made according to Synthetic Example 1, made with equal molar amounts of the following PRMs: Cymal, Cinnamic Aldehyde, Acetophenone, and Benzaldehyde, (113.3 grams) is combined with 1756.6 grams of molten polyethylene glycol (Pluriol E 8000 Prill supplied by BASF Corporation) and 119.8 grams of free fragrance. The blend is mixed and solidified into consumer product particles having an average diameter of about 0.3 cm to about 1.5cm, and/or an average mass of from about lmg to about lg.
The resulting consumer product is a plurality of particles that are suitable for addition to the wash cycle of an automatic fabric washing machine, optionally in combination with a laundry detergent.

Formulation Example 3. Liquid fabric enhancers Table 8 shows exemplary formulations of compositions according to the present disclosure. Specifically, the following compositions are liquid fabric enhancer products.
Table 8.
% Active (w/w) Ingredient Composition 1 Composition 2 Composition 3 5% 7% 8%
Quaternary ammonium ester material (Ester Quat 1)1 (Ester Quat 2)2 (Ester Quat 3)3 Pro-fragrance silicone polymer* 0.25% 0.25%
0.25%
Formic Acid 0.045% 0.045% 0%
Hydrochloric acid 0.01% 0% 0%
Preservative 0.0045% 0% 0%
Chelant 0.0071% 0.0071% 0%
Structurant 0.10% 0.30%
0.1%
Antifoam 0.008% 0.00% 0%
Water Balance Balance Balance 1 Ester Quat 1: Mixture of bis-(2-hydroxypropy1)-dimethylammonium methylsulfate fatty acid ester, (2-hydroxypropy1)-(1-methy1-2-hydroxyethyl)-dimethylammonium methylsulfate fatty acid ester, and bis-(1-methy1-2-hydroxyethyl)-dimethylammonium methylsulfate fatty acid ester, where the fatty acid esters are produced from a C12-C18 fatty acid mixture (REWOQUAT DIP V 20 M Conc, ex Evonik) 2 Ester Quat 2: N,N-bis(hydroxyethyl)-N,N-dimethyl ammonium chloride fatty acid ester, produced from C12-C18 fatty acid mixture (REWOQUAT CI-DEEDMAC, ex Evonik) 3 Ester Quat 3: Esterification product of fatty acids (C16-18 and C18 unsaturated) with triethanolamine, quaternized with dimethyl sulphate (REWOQUAT WE 18, ex Evonik) * Pro-fragrance silicone polymer premix emulsion according to Synthesis Example 1, made with equal amounts of the following PRMs: Cymal, Cinnamic Aldehyde, Acetophenone, and Benzaldehyde Formulation Example 4. Liquid laundry detergents Table 9 shows exemplary formulations of heavy-duty liquid laundry detergent compositions that may be made according to the present disclosure. Amounts provided are by weight % of active, unless otherwise indicated.
Table 9.
Ingredients 1 2 3 4 5 6 AE18S 6.77 2.16 1.36 1.30 AE3S 3.0 0.45 LAS 0.86 2.06 2.72 0.68 0.95 HSAS 1.85 2.63 1.02 AE9 6.32 9.85 10.2 7.92 35.45 AE7 8.40 12.44 C1214 dimethyl Amine 0.3 0.73 0.23 0.37 C1218 Fatty Acid 0.80 L90 0.60 0.99 1.20 15.00 Citric Acid 2.50 3.96 1.88 1.98 0.9 2.5 0.6 Optical Brightener 1 1.0 0.8 0.1 0.3 0.05 0.5 0.001 Optical Brightener 3 0.001 0.05 0.01 0.2 0.5 Sodium formate 1.6 0.09 1.2 0.04 1.6 1.2 0.2 DTI 1 0.32 0.05 0.6 0.1 0.6 0.01 DTI 2 0.32 0.1 0.6 0.6 0.05 0.4 0.2 Sodium hydroxide 2.3 3.8 1.7 1.9 1.7 2.5 2.3 Monoethanolamine 1.4 1.49 1.00 0.7 Diethylene glycol 5.5 4.1 Chelant 1 0.15 0.15 0.11 0.07 0.5 0.11 0.8 4-formyl-phenylboronic 0.05 0.02 0.01 acid Sodium tetraborate 1.43 1.50 1.10 0.75 1.07 Ethanol 1.54 1.77 1.15 0.89 3.00 7.00 Polymer 1 0.1 2.00 Polymer 2 0.3 0.33 0.23 0.17 Polymer 3 0.8 Polymer 4 0.8 0.81 0.60 0.40 1.0 1.0 1,2-Propanediol 6.6 3.3 0.5 2.0 8.0 Structurant 0.1 0.1 Perfume (neat oil) 1.6 1.1 1.0 0.8 0.9 1.5 1.6 Pro-fragrance silicone 0.1 0.1 0.2 0.1 0.1 0.1 0.3 polymer Protease 0.8 0.6 0.7 0.9 0.7 0.6 1.5 Mamanase 0.7 0.05 0.045 0.06 0.04 0.045 0.1 Amylase 1 0.3 0.1 Amylase 2 0.1 0.1 0.07 Amylase4 0.3 0.1 0.15 0.03 0.4 0.1 Isoamylase 0.3 0.2 0.1 0.07 0.2 0.02 0.3 Xyloglueanase 0.2 0.1 0.05 0.05 0.2 Lipase 0.4 0.2 0.3 0.1 0.2 Polishing enzyme 0.04 0.004 Dispersin B 0.05 0.03 0.001 0.001 Acid Violet 50 0.05 0.05 Direct Violet 9 0.05 Violet DD 0.035 0.02 0.037 0.04 Water insoluble plant 0.2 1.2 fiber Dye control agent 0.3 0.5 0.3 Alkoxylated polyaryl 1.2 3.1 polyalkyl phenol Water, dyes & minors Balance pH 8.2 = AE1.85 is C1215 alkyl ethoxy (1.8) sulfate = AE3S is C1215 alkyl ethoxy (3) sulfate = AE7 is C1213 alcohol ethoxylate, with an average degree of ethoxylation of 7 = AE8 is C1213 alcohol ethoxylate, with an average degree of ethoxylation of 8 = AE9 is C1213 alcohol ethoxylate, with an average degree of ethoxylation of 9 = Alkoxylated polyaryl is, for example, EMULSOGENS 15160, HOSTAPALSBV
conc., SAPOGENAT T110, and/or SAPOGENATO T139, all from Clariant = Amylase 1 is STAINZYMES, 15 mg active/g = Amylase 2 is NATALASE0, 29 mg active/g = Amylase 3 is STAINZYN1E PLUS , 20 mg active/g = Isoamylase has glycogen-debranching activity = AS is C1214 alkylsulfate = Cellulase 2 is CELLUCLEAN , 15.6 mg active/g = Xyloglucanase is WHITEZYMES, 20 mg active/g = Chelant 1 is diethylene triamine pentaacetic acid (DTPA) = Chelant 2 is 1-hydroxyethane 1,1-diphosphonic acid (HEDP) = Chelant 3 is sodium salt of ethylenediamine-N,N'-disuccinic acid, (S,S) isomer (EDDS) = Dispersin B is a glycoside hydrolase, reported as 1000 mg active/g = DTI 1 is poly(4-vinylpyridine-l-oxide), such as CHROMABOND S-403ES), = DTI 2 is poly(1-vinylpyrrolidone-co-l-vinylimidazole) (such as SOKALAN
HP56 C).
= Dye control agent is, for example, SUPAREXO 0.IN (M1), NYLOFDCANS P (M2), NYLOFDCANS PM (M3), or NYLOFDCANS HF (M4) = HSAS is mid-branched alkyl sulfate as disclosed in U.S. Pat. No.
6,020,303 and U.S. Pat.
No. 6,060,443 = LAS is linear alkylbenzenesulfonate having an average aliphatic carbon chain length C9-C15 (HLAS is acid form) = Lipase is LIPEX , 18mg active/g = Mannanase is MANNAWAYS, 25 mg active/g = Optical Brightener 1 is disodium 4,4'-bis{ [4-anilino-6-morpholino-s-triazin-2-y1]-amino}-2,2-stilbenedisulfonate = Optical Brightener 2 is disodium 4,4'-bis-(2-sulfostyryl)biphenyl (sodium salt) = Optical Brightener 3 is OPTIBLANC SPL10 from 3 V Sigma = Photobleach is a sulfonated zinc phthalocyanine = Polishing enzyme is Para-nitrobenzyl esterase, reported as 1000 mg active/g = Polymer 1 is bis((C2H50)(C2H40)n)(CH3) -N -CH----N'----(CH3)-bis((C2H50)(C21140)n), wherein n = 20-30, x = 3 to 8, or sulphated or sulfonated variants thereof = Polymer 2 is ethoxylated (E015) tetraethylene pentamine = Polymer 3 is ethoxylated polyethylenimine (PEI600 E020) = Polymer 4 is ethoxylated hexamethylene diamine = Polymer 5 is ACUSOL 305, provided by Rohm&Haas 5 = Polymer 6 is a polyethylene glycol polymer grafted with vinyl acetate side chains, provided by BASF
= Pro-fragrance silicone polymer premix emulsion is Synthetic Example 6, made with equal amounts of the following PRMs: Cymal, Cinnamic Aldehyde, Acetophenone, and Benzaldehyde 10 = Protease is PURAFECT PRIME , 40.6 mg active/g = Protease 2 is SAVINASE , 32.89 mg active/g = Protease 3 is PURAFECT , 84 mg active/g = Quaternary ammonium is C1214 Dimethylhydroxyethyl ammonium chloride = S-ACMC is Reactive Blue 19 Azo-CM-Cellulose, provided by Megazyme 15 = Soil release agent is REPEL-O-TEX SF2 = Structurant is Hydrogenated Castor Oil = Violet DD is a thiophene azo dye provided by Milliken = Water insoluble plant material is, for example, Herbacel AQ+ Type N, supplied by Herbafood Ingredients GmbH, Werder, Germany 20 Formulation Example 5. Unit dose articles Table 10 shows formulations of various unit dose detergent articles in the form of pouches.
Multi-compartment pouches can contain a plurality of benefit agents. By way of a non-limiting example, a two- or three-component pouch may contain the formulations presented in Table 10 in separate enclosures, where dosage is the amount of the formulation in the respective enclosure.
25 The pouch may be formed from a water-soluble film, such as polyvinyl alcohol films available from MonoSol, LLC (Indiana, USA).
Table 10.
A
3 compartments 2 compartments 3 compartments Compartment # 1 2 3 1 2 1 Dosage (g) 34.0 3.5 3.5 30.0 5.0 25.0 1.5 4.0 Ingredients Weight %
Alkylbenzene sulfonic acid 20.0 20.0 20.0 10.0 20.0 20.0 Alkyl sulfate 2.0 C12-14 alkyl 7-ethoxylate 17.0 17.0 17.0 17.0 17.0 Cationic surfactant 1.0 Zeolite A 10.0 C12-18 Fatty acid 13.0 13.0 13.0 18.0 18.0 Sodium acetate 4.0 enzymes 0-3 0-3 0-3 0-3 0-3 Sodium Percarbonate 11.0 TAED 4.0 A
3 compartments 2 compartments 3 compartments Organic catalyst 1.0 PAP granule 2 Polycarboxylate 1.0 Polyethyleneimine ethoxylate 3 2.2 2.2 2.2 Hydroxyethane diphosphonic acid 0.6 0.6 0.6 0.5 Ethylene diamine tetra(methylene 0.4 phosphonic) acid Brightener 0.2 0.2 0.2 0.3 0.3 Mineral oil Hueing dye4 0.05 0.035 0.12 Perfume (neat) 1.7 1.7 0.6 1.5 Fragrance Premix* 3 2.5 3 Water and minors (antioxidant, 10.0 10.0 10.0 4.0 aesthetics, etc.) Buffers (sodium To p11 8.0 for liquids carbonate, monoethanolamine) 5 To RA > 5.0 for powders Solvents (1,2 propanediol, To 100%
ethanol) for liquids, sodium sulfate for powders 1 Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-y1)-1-(2-ethyl-hexyloxymethyl)-ethyliester as described in US7169744 2 PAP = Phtaloyl-Amino-Peroxycaproic acid, as a 70% active wet cake 3 Polyethylenimine (MW = 600) with 20 ethoxylate groups per -NH.
4 Ethoxylated thiophene, EO (Ri+R2) = 5 5 RA = Reserve Alkalinity (g NaOH/dose) * A silicone/PRM premix emulsion according to the present disclosure. Wt%
provided in table is the amount of fragrance premix provided, not the amount of perfume delivered by the premix;
premix is substantially free of water. The premix is made with about 20% of perfume raw materials, by weight of the premix.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."
Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention.
Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

93What is claimed is:

1. A treatment composition comprising a treatment adjunct and a pro-fragrance silicone polymer, wherein the pro-fragrance silicone polymer comprises a silicone backbone, an organic linker group comprising a carbon atom bonded to a silicon atom of the silicone backbone, and a heterocyclic moiety bonded to the organic linker group, the heterocyclic moiety comprising from five to seven ring members, the ring members comprising:
a first ring member that is a nitrogen atom;
a second ring member that is a carbon atom, wherein the second ring member is part of a residue of a perfume raw material ("PRM"), wherein the PRM that formed the residue comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and a combination thereof;
a third ring member selected from the group consisting of an oxygen atom or a sulfur atom, preferably an oxygen atom, wherein the second ring member is directly bonded to the first ring member and to the third ring member.

2. The treatment composition according to claim 1, wherein the pro-fragrance silicone polymer comprises at least one radical selected from the group consisting of Formula 1, Formula II, and mixtures thereof, wherein the radicals of Formula I and Formula II have the following structures:
(Si) ¨ X ¨ Z Formula I
(Si) ¨ X ¨ (Z ¨ ¨ (Si) Formula II
wherein "(Si) ¨" represents the bond to an Si atom, wherein each X group is the organic linker group and is an independently selected divalent organic moiety group comprising from two to twenty-four chain atoms, wherein the Z group comprises the heterocyclic moiety, and wherein the index n is 1 or 2, preferably 1, preferably wherein the at least one radical has the structure of Formula I.

3. The treatment composition according to any preceding claim, wherein the PRM
that formed the residue comprises an aldehyde moiety, preferably wherein the PRM is selected from the group consisfing of: methyl nonyl acetaldehyde: benzaldehyde; floralozone; isocyclocitral; triplal (ligustral);
precylcemone B; lilial; decyl aldehyde; undecylenic aldehyde; cyclamen homoaldehyde;
cyclamen aldehyde; dupical; oncidal; adoxal; rnelonal; calypsone; anisic aldehyde;
heliotropin;
cuminic aldehyde; scentenal; 3,6-dimethylcyclohex-3-ene-1-carbaldehyde;
satinaldehyde;
canthoxal; vanillin; ethyl vanillin; cinnarnic aldehyde; and mixtures thereof.

4. The treatment composition polymer according to any preceding claim, wherein the PRM that formed the residue comprises a ketone moiety, preferably wherein the PRM is selected from the group consisfing of:
nerolione; 4-(4-methoxyphenyl)butan-2-one; 1 -naphthalen-2-ylethanone; nectaryl; trimofix 0;
fleuramone; delta-damascone; beta-darnascone; alpha-damascone; methyl ionone;

hexylcyclopent-2-en-1-one; galbascone; and mixtures thereof.

5. The treatment composition according to any of claims 2-4, wherein each X
group independently comprises from two to twelve chain atoms, preferably frorn two to twelve chain atoms, more preferably from two to nine chain atoms, more preferably from two to six chain atoms, even more preferably wherein at least one of the chain atoms is an oxygen atom, even more preferably wherein the X
group is a four-carbon ether group, most preferably wherein the X group is -CH2-0-CH2-.

6. The treatment composition according to any of claims 2-5, wherein the X
group is bonded to a non-terrninal silicon atom.

7. The treatment cornposition according to of claims 2-6, wherein each Z is a monovalent or divalent heterocyclic rnoiety according to Formula TIE, wherein formula III has the following structure:

(J )m / \
R1¨N
\ /G
C
/ \

Formula III, wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen, wherein the index m is from 2 to 4, preferably m is from 2 to 3, more preferably m is 2, wherein R1 is selected from H, a monovalent moiety with a molecular weight of from 15 to 495 Da, or a point of attachment of Z to an X group, preferably wherein R1 is H or a point of attachment of Z to an X group, wherein when R1 is present as the monovalent moiety, the monovalent moiety is preferably a substituted or unsubstituted C1-C35alkyl group, more preferably a monovalent moiety with a molecular weight of from 15 to 101 Da, even more preferably a substituted or unsubstituted C1-C8 alkyl, wherein each J is independently selected from the group consisting of C(R2)2, -0-, -N(R2)-, wherein each R2 is independently selected from H, a monovalent moiety with a molecular weight of from 14 to 990 Da, or a point of attachment of Z to an X group, wherein when R2 is present as the monovalent moiety, the monovalent moiety is preferably a substituted or unsubstituted, saturated or unsaturated CI-Cm alkyl, more preferably a monovalent moiety with a molecular weight of from 14 to 186 Da, even more preferably a substituted or unsubstituted, saturated or unsaturated Ci to C12 alkyl, preferably R2 is H or a point of attachment of Z to an X group, with the proviso that a fffst unit and a second unit can optionally be taken together, where feasible, as a divalent substituent, where the fffst unit is a first R2 group, and where the second unit is selected from the group consisting of a second R2 group, the R1 group, and a monovalent substituent of the R1 group, preferably where the divalent substituent is selected from the group consisting of a fused ring, a spirocyclic ring, an unsaturated substituent, =N(R1), =0, and =S, wherein the -C(Ie)(R4)- moiety is the residue of a perfume raw material (PRM), preferably a PRM that comprises from 3 to 34 carbon atoms, wherein the perfume raw material from which the residue is derived comprises an aldehyde moiety, a ketone moiety, or a combination thereof, preferably wherein IV is independently selected from a monovalent organic moiety, and preferably wherein is R4 is independently selected from the group consisting of hydrogen and a monovalent organic moiety, provided that at least one and no more than two of R1, any R2, or mixtures thereof are a point of attachment of Z to an X group.

8. The treatment composition according to any of claims 2-7, wherein each Z is a monovalent or divalent five-membered heterocyclic moiety according to Formula IV, wherein formula IV has the following structure:
1J ---.

µC'G

Formula IV, wherein G, R1, R3, and R4 are as described above, preferably wherein G is oxygen, and wherein each J is independently C(R2)2, wherein R2 is as described above.

9. The treatment composition according to any of claims 7-8, wherein two of R1, any R2, or a combination thereof are points of attachment of Z to an X group, preferably forming a second ring structure.

10. The treatment composition according to any of claims 7-9, wherein each Z
is a monovalent or divalent heterocyclic moiety according to Formula III or Formula IV, preferably a five-membered heterocyclic moietyä wherein at least one le is a point of attachment of Z to an X
group, preferably wherein R1 is H.

11. The treatment composition according to any preceding claim, wherein the pro-fragrance silicone polymer has the following structure:
[R5R6R7Si01/21(q+2r+2) [R8R9Si02/2], [R10S103/2],i rSiO4/21r Formula V
wherein:
q is an integer from 0 to 150, p is an integer from 0 to 1500, r is an integer from 0 to 150, wherein q+p+r equals an integer greater than or equal to 1;
each of R5, R6, R7, R8, R9 and R1 moiety is independently selected from the group consisting of H, OH, a monovalent organic moiety, a radical according to Formula I, or a radical according to Formula II, wherein at least one of the R5-R1 moieties is a radical according to Formula I or a radical according to Formula II, preferably a radical according to Formula I.

12. The treatment composition according to any preceding claims, wherein the treatment adjunct is selected from the group consisting of an amine, a surfactant system, a water-binding agent, a sulfite, fatty acids and/or salts thereof, enzymes, encapsulated benefit agents, soil release polymers, hueing agents, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzyme stabilizers, catalytic materials, bleaching agents, bleach catalysts, bleach activators, polymeric dispersing agents, soil removal/anti-redeposition agents, polymeric dispersing agents, polymeric grease cleaning agents, brighteners, suds suppressors, dyes, free perfume, structure elasticizing agents, conditioning or softening agents, carriers, fillers, hydrotropes, organic solvents, anti-malodor agent, anti-microbial agents and/or preservatives, neutralizers and/or pH
adjusting agents, processing aids, fillers, rheology modifiers or structurants, opacifiers, pearlescent agents, pigments, anti-corrosion and/or anti-tarnishing agents, and mixtures thereof, preferably wherein the treatment adjunct comprises a surfactant system, conditioning or softening agents, or a mixture thereof, more preferably wherein the surfactant system, if present, comprises anionic surfactant, nonionic surfactant, cationic surfactant, and/or zwitterionic surfactant, and/or more preferably wherein the conditioning or softening agents, if present, comprise a quaternary ammonium compound, silicone compounds, or both.

13. A liquid premix composition comprising:
a) a pro-fragrance silicone polymer as described in any of claims 1-12, optionally, further comprising one or more free perfume raw materials; or b) a precursor silicone polymer, and a perfume raw material that comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and a combination thereof, wherein the precursor silicone polymer and the perfume raw material are capable of condensing to form the pro-fragrance silicone polymer as described in any of claims 1-12; or c) a mixture thereof.

14. The liquid premix composition according to claim 13, wherein the liquid premix composition is in the form of an oil-in-water emulsion, preferably comprising droplets characterized by a volume-weighted average particle size of from about 100 nm to about 100 gm, more preferably from 1 gm to 10 gm, even more preferably from 1 gm to 5 gm.

15. The liquid premix composition according to any of claims 13-14, wherein, by weight of the liquid premix composition, the precursor silicone polymer is present at a level of from about 1% to about 99%, preferably from about 80% to about 10%, or from about 75% to about 20%, or from about 60% to 40%, and the perfume raw material is present at a level of from about 1% to 50%, preferably from about 5% to about 50%, or from about 5% to about 40%, or from about 5% to about 30%, or from about 5% to about 20%, or from about 5% to about 15%, or from about 5%
to about 10%, preferably wherein the weight ratio of the precursor silicone polymer and the perfume raw material is from about 99:1 to about 1:1, preferably from about 50:1 to about 2:1, more preferably from about 10:1 to about 5:1.

16. The liquid premix composition according to any of claims 13-15, wherein the precursor silicone polymer comprises at least one radical selected from the group consisting of Formula VI, Formula VII, and mixtures thereof, wherein the radicals of Formula VI and Formula VII have the following structures:
(Si) ¨ X ¨ Y Formula VI;
(Si) ¨ X ¨ (Y ¨ X). ¨ (Si) Formula VII;
wherein "(Si) ¨" is the bond to an Si atom, wherein the index n is 1 or 2, preferably 1, wherein each X group is covalently linked to "(Si)" via a Si-C bond and is an independently selected divalent organic group comprising from two to twenty-four chain atoms, and wherein each Y is independently a monovalent or divalent moiety according to Formula VIII, wherein Formula VIII has the following structure:
Formula VIII, wherein G is selected from the group consisting of oxygen or sulfur, preferably oxygen, wherein the index m is from 2 to 4, preferably m is from 2 to 3, more preferably m is 2, wherein IV is selected from H, a monovalent moiety with a molecular weight between 15 and 500 Da, or a point of attachment of Y to an X group, wherein when Ft' is present as the monovalent moiety, the monovalent moiety is preferably a substituted or unsubstituted C1-C35alkyl group, more preferably a monovalent moiety with a molecular weight of from 15 to 101 Da, even more preferably a substituted or unsubstituted C1-C8 alkyl, preferably wherein R1 is H, wherein each J is independently selected from the group consisting of C(R2)2, -0-, -N(R2)-, wherein each R2 is independently selected from the group consisting of H, a monovalent moiety with a molecular weight between 14 and 990 Da, or a point of attachment of Y to an X group, wherein when R2 is present as the monovalent moiety, the monovalent moiety is preferably a substituted or unsubstituted, saturated or unsaturated C1-C70 alkyl, more preferably a monovalent moiety with a molecular weight of from 14 to 186 Da, even more preferably a substituted or unsubstituted, saturated or unsaturated C1 to C12 alkyl, preferably wherein each R2 is H, with the proviso that a first unit and a second unit can optionally be taken together, where feasible, as a divalent substituent, where the first unit is a first R2 group, and where the second unit is selected from the group consisting of a second R2 group, the R1 group, and a monovalent substituent of the R1 group, preferably where the divalent substituent is selected from the group consisting of a fused ring, a spirocyclic ring, an unsaturated substituent, =N(R2), =0, and =S, provided that at least one and no more than two of IV, any R2, or combinations thereof is a point of attachment of Y to an X group.

17. A method of making a treatment composition, the method comprising the steps of:
providing a base composition, wherein the base composition comprises a treatment adjunct;
combining the base composition with one or more of the following:
a) a pro-fragrance silicone polymer as described in any of claims 1-12;

ioi b) a precursor silicone polymer as described in any of claims 13-16, and a perfume raw material that comprises a moiety selected from the group consisting of an aldehyde moiety, a ketone moiety, and a combination thereof, preferably wherein the precursor silicone polymer and the perfume raw material are provided together as a liquid premix composition, preferably a liquid premix composition in the form of an emulsion; or c) a mixture thereof.

18. Use of a pro-fragrance silicone polymer as described in any of claims 1-12 as a perfuming agent, optionally on a surface, preferably on a fabric, optionally being formulated in a treatment composition, where the treatment composition may be a treatment composition according to any of claims 1-12.